Multi-layer dry paint decorative laminate having discoloration prevention barrier

ABSTRACT

A decorative dry paint transfer laminate includes a layer of dry paint, a pressure-sensitive adhesive layer on one side of the dry paint layer, and a release liner in releasable contact with the dry paint layer on a side opposite from the pressure-sensitive adhesive (PSA). The release liner has a matte release coat layer that contacts the dry paint layer. The release liner is released from the dry paint layer after the PSA side is attached to a surface. The matte release coat adheres to the dry paint layer to provide a protective function but also to transfer a decorative matte finish to the dry paint layer when the release liner is removed from it. The laminate includes a barrier layer to protect against significant discoloration of the color in the dry paint layer caused by migration of mono azo pigments from a painted surface.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This is a continuation-in-part of U.S. application Ser. No.457,826, filed Jun. 9, 2003, which is a continuation-in-part of U.S.application Ser. No. 367,611, filed Feb. 14, 2003. These applicationsare incorporated herein in their entirety by this reference.

FIELD OF THE INVENTION

[0002] This invention relates generally to dry paint transfer laminates,and more particularly, to a multi-layer dry paint decorative laminatehaving a barrier layer that inhibits migration of discoloration-causingpigments into color-producing layers of the laminate.

BACKGROUND

[0003] Dry paint transfer laminates have been used in the past assurface coverings that provide an alternative to conventional painting.Water based paints and oil based paints have well known shortcomingsthat can be overcome by the use of decorative dry paint transfer filmsas a paint replacement. Environmental problems such as solventevaporation from paint systems applied by spray painting also areavoided by use of decorative dry paint transfer films.

[0004] Such decorative dry paint transfer films are typically applied toa substrate surface by an adhesive layer carried by the film. Use ofheat-activated adhesives or water-activated adhesives can have certaindisadvantages that are overcome by use of pressure-sensitive adhesives,by which the decorative film is adhered to the substrate surface byapplication of pressure only, typically at room temperature. Examples ofdecorative films having pressure-sensitive adhesive layers for interioror exterior applications are disclosed in U.S. Pat. No. 6,096,396 toPatton et al., U.S. Pat. No. 6,086,995 to Smith, and U.S. Pat. No.5,229,207 to Paquette et al.

[0005] Decorative films having a pressure-sensitive adhesives are oftenadapted to facilitate application to a surface by using various forms ofrepositionable adhesives known in the art. The laminate can be initiallyapplied to a surface, removed temporarily, and then repositioned, toallow the adhesive to form a permanent bond. Decorative films havingsuch a repositionable adhesive layer are described, for example, in the'207 patent to Paquette et al.

[0006] The present invention comprises a multi-layer laminate adapted tobe placed in contact with a surface which can be a painted surface. Infilms overlaying painted surfaces containing pigmented materials such asdyes or mono azo pigments, the colored materials may migrate or bleedinto the overlaying film. This causes the finish to discolor. Pigmentsused in wall paints containing yellow pigments as a component, or to alesser extent, orange or red pigments or dyes, can contain such mono azoconstituents that can migrate from the wall surface through the overlaidfilm and into the color layer of the film, causing it to discolor.

[0007] The present invention provides a multi-layer laminate adapted forcontact with a painted substrate surface containing organic materialswith color constituents that will bleed or migrate; and the inventionaddresses a situation, in particular, where the painted surfacecontaining the migrating organic color components may not be modified toavoid the color migration problem. In response to this problem, theinvention provides a laminate containing one or more barrier layers thatcooperate to block or capture the migrating color materials, and inparticular, those containing mono azo pigments. The barrier layerinhibits discoloration of the colored layer or layers in the laminatecaused by the laminate contacting such a painted surface.

SUMMARY OF THE INVENTION

[0008] Briefly, the invention comprises a multi-layer laminate adaptedto provide a layer of. color to a painted surface. The laminate includesa pressure-sensitive adhesive for overlaying and contacting the paintedsurface. The laminate includes one or more barrier layers that slow orstop the migration of discoloration-causing pigments from the surface,through the adhesive layer, to the color layer of the laminate.

[0009] In one embodiment, the barrier will slow or stop the color changecaused by mono azo pigments in interior latex paint. By applying abarrier layer of specific polymers and/or by addition of specificadditive materials to the barrier layer, the color migration may bestopped or significantly reduced.

[0010] One embodiment of the invention comprises a decorative dry painttransfer laminate having a layer of dry paint, a pressure-sensitiveadhesive layer on one side of the dry paint layer, and a release linerin releasable contact with the dry paint layer on a side opposite fromthe pressure-sensitive adhesive. The dry paint layer comprises a binderand a pigment. A barrier layer is positioned between the dry paint layerand the pressure-sensitive adhesive layer. The release liner isremovable from the dry paint layer at room temperature. Thepressure-sensitive adhesive is adapted for adhering the laminate to asubstrate surface at room temperature. The substrate surface can be apainted wall surface containing organic materials with color that canbleed or migrate. The pressure-sensitive adhesive layer adheres thelaminate to the substrate surface under application of pressure. Therelease liner is then peeled away from the dry paint layer. The barrierlayer comprises a thin, flexible film made from a material that stops orappreciably reduces migration of discoloration-causing constituentsmigrating from the painted surface through the adhesive layer to thecolor layer. In one embodiment, the barrier layer can comprise apolymeric material having a cross-linking density sufficient to inhibittransmission of discoloration-causing pigments and/or a dispersedadditive that may capture or retard the migration ofdiscoloration-causing pigments. The barrier layer is particularly usefulin retarding or inhibiting the transmission of azo-type pigments and ispresent at a low coat weight or thickness which does not significantlyincrease the overall thickness of a decorative film. In one embodiment,the barrier thickness is no more than about 10% of the total thicknessof the decorative film (excluding the outer releasable carrier film).

[0011] These and other aspects of the invention will be more fullyunderstood by referring to the following detailed description and theaccompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

[0012]FIG. 1 is a schematic cross-sectional view illustrating oneembodiment of a multi-layer dry paint transfer laminate according toprinciples of this invention.

[0013]FIG. 2 is a schematic illustration of the dry paint transferlaminate self-wound into a roll form.

[0014]FIG. 3 is a schematic cross-sectional view showing an alternativeembodiment of a dry paint layer contained in the laminate.

[0015]FIG. 4 is a schematic cross-sectional view showing anotheralternative embodiment of the dry paint layer.

[0016]FIG. 5 is a schematic cross-sectional view illustrating analternative embodiment of the dry paint layer of FIG. 4.

[0017]FIG. 6 is a schematic cross-sectional view illustrating anembodiment containing a support layer.

[0018]FIG. 7 is a schematic cross-sectional view illustrating anembodiment containing a barrier layer.

[0019]FIG. 8 is a schematic illustration of a process for co-extruding asupport layer and an adhesive layer used in one embodiment of theinvention.

[0020]FIG. 9 is a schematic illustration of a process for co-extruding asupport layer and an adhesive layer used in another embodiment of theinvention.

[0021]FIG. 10 is a schematic view illustrating one embodiment of theinvention which includes a dry paint layer, a barrier layer and a tiecoat for the adhesive layer.

DETAILED DESCRIPTION

[0022] Referring to FIG. 1, a multilayer dry paint transfer laminate 20is adapted for use as a surfacing film. The multilayer laminate includesa pigmented dry paint layer 22 comprising a synthetic resinous bindercontaining a dispersed pigment. The dry pigmented paint layer 22, alsoreferred to herein as a color layer, generally can be a monocoatpigmented layer as illustrated in FIG. 1, or it can be combined withadditional pigmented paint layers, coatings or print coats describedbelow. In each instance, these decorative elements of the multilayer drypaint transfer film will be referred to generally as a decorative drypaint layer. In the illustrated FIG. 1 embodiment, the dry paint layer22 has an upper surface 24 and a lower surface 26. The multilayerlaminate further includes a dry adhesive layer 28 overlying and adheredto the upper surface 24 of the dry paint layer, and a flexible andfoldable release liner 30 overlying and releasably adhered to the lowersurface of the dry paint layer. The release liner has a matte releasecoat 32 on its inner surface for releasably adhering the release liner30 to the lower surface 26 of the dry paint layer 22. The release liner30 is adapted to be peeled away from the dry paint layer under anapplied release force, also referred to herein as a carrier releasefunction. The matte release coat 32 separates from the dry paint layer22 but remains adhered to the release liner 30 when the release liner ispeeled away from the dry paint layer. The release liner 30 also has anadhesive release coat layer 34 on a surface opposite from the dry paintlayer. An exposed outer surface 38 of the adhesive release coat layer 34is adapted for releasably contacting an exposed outer surface 40 of theadhesive layer 28 when the laminate is wound in a roll form illustratedin FIG. 2.

[0023] Referring to FIG. 2, the dry paint transfer laminate 20 isself-wound into a roll form with the outer exposed surface 38 of theadhesive release coat layer 34 in releasable contact with the exposedouter surface 40 of the adhesive layer 28. Thus, when the dry painttransfer laminate 20 illustrated in FIG. 2 is unwound, the adhesiverelease coat layer 34 on the release liner separates from the outersurface 40 of the adhesive layer 28 and remains adhered to the releaseliner 30. The matte release coat 32 remains adhered to the dry paintlayer.

[0024]FIG. 3 illustrates a dry paint transfer laminate 42 which isidentical to the dry paint transfer laminate 20 illustrated in FIG. 1,except that the decorative dry paint layer includes an opticallytransparent synthetic resinous clear coat layer 44 adhered to the lowersurface 26 of the pigmented dry paint layer 22. In this embodiment, theouter clear coat layer 44 is in releasable contact with the matterelease coat 32 of the release liner 30. When the release liner 30 ispeeled away from the clear coat layer 44, the matte release coat 32separates from the clear coat layer 44 and remains adhered to therelease liner 30.

[0025]FIG. 4 illustrates a multilayer dry paint transfer laminate 46which is identical to the dry paint transfer laminate 42 illustrated atFIG. 3, except that the decorative dry paint layer further includes adecorative print coat layer 48 between the pigmented dry paint layer 22and the clear coat layer 44. The decorative print coat layer provides adecorative print pattern, and the pigmented dry paint layer 22 providesa background color and opacity for the decorative dry paint layer. Theprint pattern and background color are visible through the outer clearcoat layer 44.

[0026]FIG. 5 illustrates a multilayer dry paint transfer laminate 50which is identical to the dry paint transfer laminate 46 illustrated inFIG. 4, except that a second decorative print coat layer 52 can beprinted or coated between the print coat layer 48 and the outer clearcoat layer 44.

[0027] Additional print coat layers may be used. For instance, themultilayer laminate may contain up to about five or more print coats,and in one embodiment, preferably three or four print coat layers areused. The layers may have a print or design pattern using conventionalprinting methods, such as gravure, flexography, silk screen, or ink jetprinting.

[0028]FIG. 6 illustrates an embodiment of a multilayer dry painttransfer laminate 54 which is identical to the multilayer laminate 20illustrated in FIG. 1, except that the laminate 54 includes a flexiblereinforcing layer 56 (also referred to herein as a support layer)between the dry paint layer 22 and the adhesive layer 28. Thereinforcing layer 56 provides a means of structural support for thedecorative dry paint layer and can provide additional opacity for thedecorative dry paint layer. The reinforcing layer has a tensile strengthwhich exceeds that of the dry paint layer or layers.

[0029]FIG. 7 illustrates another embodiment of the dry paint transferlaminate 58 which is identical to the laminate 20 illustrated in FIG. 1,except that the laminate 58 includes a flexible barrier layer 60 betweenthe pigmented dry paint layer 22 and the adhesive layer 28. Theintervening barrier layer can be used to inhibit or prevent undesiredmigration of constituents between the adhesive layer and the paint coatlayer. Such barrier properties can include reducing or avoidingundesired discoloration by inhibiting or preventing migration ofpigments from an underlying substrate surface through the adhesive layerto the dry paint layer.

[0030] The embodiment of FIGS. 6 and 7 show separate support(reinforcing) and barrier layers. In addition, the barrier layer 60 maybe included as a layer in the FIG. 6 embodiment. In this instance, thebarrier layer may be applied between the dry paint layer and the support(reinforcing) layer, or the barrier layer may be applied between theadhesive layer and the support layer.

[0031] The dry paint layer 22 may have a thickness generally of about0.5 to about 1.5 mils, in one embodiment about 0.5 to about 1.2 mils,and in another embodiment from about 0.5 to about 0.9 mil. The thicknessof the adhesive layer may range generally from about 0.4 to about onemil, in one embodiment from about 0.4 to about 0.8 mil, and in anotherembodiment from about 0.4 to about 0.6 mil. The thickness of the releaseliner may range generally from about 0.5 to about 2 mils, in oneembodiment from about 0.5 to about 1.5 mils, and in another embodimentfrom about 0.85 to about 1.05 mils. The thickness of the matte releasecoat layer may range generally from about 0.05 to about 0.3 mil, and inone embodiment from about 0.1 to about 0.2 mil. The thickness of theadhesive release coat layer may range from about 0.04 to about 0.2 mil,in one embodiment from about 0.04 to about 0.15 mil, and in anotherembodiment from about 0.04 to about 0.08 mil. The thickness of the outerclear coat layer may range generally from about 0.05 to from about 0.4mil, and in one embodiment from about 0.05 to about 0.3 mil.

[0032] The thickness of the decorative print coat layers may range fromabout 0.02 to about 0.15 mil, and in one embodiment from about 0.02 toabout 0.08 mils.

[0033] The reinforcing layer may have a thickness generally of about 0.3to about 1.4 mils. In one embodiment the thickness can be about 0.3 toabout 1.1 mils, in another embodiment about 0.3 to about 0.8 mil, and ina further embodiment about 0.3 to about 0.5 mil. When the reinforcinglayer is used, the overall thickness of the combination of the dry paintlayer and the support layer may be in the range of about 0.5 to about1.5 mils, in another embodiment about 0.5 to about 1.2 mils, and in afurther embodiment from about 0.5 to about 0.9 mil.

[0034] The barrier layer may have a thickness in the range of about 0.01to about 0.1 mil, and in one embodiment about 0.05 to about 0.1 mil, andin another embodiment from about 0.01 to about 0.02 mil.

[0035] Each of the foregoing thicknesses are dry film thicknesses. Thelaminates may have any width or length that is suitable for its end use.For example, the width may range from about one to about 200 cm, and inone embodiment from 10 to 100 cm, and in another embodiment from about30 to about 40 cm. The length may range from about 10 to about 6500meters, and in one embodiment from about 15 to about 1000 meters. Thelaminates may take the form of flat sheets or as a self-wound roll formas illustrated in FIG. 2.

[0036] Dry Paint Layer

[0037] The dry paint layers may comprise independently one or morepolymeric binders or resins, and one or more pigments. The reinforcinglayer and barrier layer may comprise one or more polymeric binders orresins, and optionally one or more pigments. The transparent outer clearcoat layer may comprise one or more polymeric binders or resins. Theselayers may be made from solvent cast liquid coating or paintcompositions comprising the one or more binders or resins and one ormore pigments (if used). These compositions may be dispersed in water orone or more organic solvents, and optionally may contain one or moreadditional additives for controlling properties such as Theologicalproperties or barrier properties. The dry paint layers, or thetransparent outer clear coat layer, or the reinforcing layer or barrierlayer may each comprise independently one or more extruded layers.

[0038] The binder or resin may comprise any binder or resinconventionally used in coating or paint formulations. The binder maycomprise a thermoplastic or thermosetting resin. The binder or resin maybe a synthetic resin or a natural resin. The binder or resin maycomprise a film forming material which may be cast as a solvent-basedcoating or in one embodiment may be an extrudable film forming material.Examples of useful binders or resins generally include acrylic, vinyl,polyester, alkyd, butadiene, styrene, urethane and epoxy resins andphthalic acid or anhydride resins, and mixtures thereof. Morespecifically, the binder or resin may include one or more polystyrenes,polyolefins, polyamides, polyesters, polycarbonates, polyvinyl chloride,polyvinyl alcohol, polyethylene vinyl alcohol, polyurethanes,polyacrylates, polyvinyl acetates, ionomer resins, and mixtures thereof.

[0039] The binder or resin may comprise vinyl and vinylidene polymers orcopolymers containing units such as vinyl acetate, vinyl chloride, andvinylidene chloride; hydrocarbon polymers and copolymers containingethylene or propylene units and oxygenated or halogenated derivatives ofether, butadiene, oxygenated butadiene, isoprene, oxygenated isoprene,butadiene-styrene, butadiene vinyl toluene, and isoprene-styrene;polymers or copolymers containing units of acrylic acid, methacrylicacid, their esters, or acrylonitrile; vinylic hydrocarbon monomersreacted with unsaturated materials such as the reaction product ofmaleic acid or anhydride with styrene; and, broadly, various otherresinous rubber-like elastomeric latex polymers and copolymers ofethylenically unsaturated monomers and polymers obtainable in stableaqueous latex form. The binder or resin may comprise a copolymer ofvinyl chloride and vinyl acetate.

[0040] The polyolefins may be characterized as having a melt index ormelt flow rate of less than about 30, and in one embodiment less thanabout 20, and in one embodiment less than about 10 as determined by ASTMTest Method 1238. The polyolefins include polymers and copolymers ofethylene, propylene, 1-butene, etc., or blends of mixtures of suchpolymers and copolymers.

[0041] Various polyethylenes may be used including low, medium, and highdensity polyethylenes. The low density range for the polyethylenes maybe from about 0.910 to about 0.925 g/cm³, the medium density range maybe from about 0.925 to about 0.940 g/cm³, and the high density range maybe from about 0.940 to about 0.965 g/cm³. An example of a useful lowdensity polyethylene is Rexene 1017 available from Huntsman.

[0042] The propylene homopolymers which may be used either alone or incombination with a propylene copolymer include a variety of propylenehomopolymers such as those having melt flow rates from about 0.5 toabout 20 as determined by ASTM Test D 1238, condition L.

[0043] The polyamide resins include resins available from EMS AmericanGrilon Inc., Sumter, S.C. under the general tradename Grivory such asCF-65, CR-9, XE-3303 and G-21. The polyamide resins also include thoseavailable from, for example, Union Camp of Wayne, N.J. under the Uni-Rezproduct line, and dimer-based polyamide resins available from Bostik,Emery, Fuller, and Henkel (under the Versamid product line).

[0044] The polystyrenes include homopolymers as well as copolymers ofstyrene and substituted styrene such as alpha-methyl styrene. Examplesof styrene copolymers and terpolymers include:acrylonitrile-butene-styrene (ABS); styrene-acrylonitrile copolymers(SAN); styrene butadiene (SB); styrene-maleic anhydride (SMA); andstyrene-methyl methacrylate (SMMA); etc.

[0045] The polyurethanes include aliphatic as well as aromaticpolyurethanes.

[0046] The polyesters may be prepared from various glycols or polyolsand one or more aliphatic or aromatic carboxylic acids. Polyethyleneterephthalate (PET) and PETG (PET modified with cyclohexanedimethanol)are useful film forming materials which are available from a variety ofcommercial sources including Eastman. For example, Kodar 6763 is a PETGavailable from Eastman Chemical. Another useful polyester from DuPont isSelar PT-8307 which is polyethylene terephthalate.

[0047] Acrylate polymers and copolymers and alkylene vinyl acetateresins (e.g., EVA polymers) may be used. Examples include EscoreneUL-7520 (Exxon), a copolymer of ethylene with 19.3% vinyl acetate;Nucrell 699 (DuPont), an ethylene copolymer containing 11% ofmethacrylic acid, etc.

[0048] Ionomer resins (polyolefins containing ionic bonding of molecularchains) may be used. Examples of ionomers include ionomeric ethylenecopolymers such as Surlyn 1706 (DuPont) and Surlyn 1702 from DuPont.

[0049] Polycarbonates also are useful, and these are available from theDow Chemical Co. (Calibre) G.E. Plastics (Lexan) and Bayer (Makrolon).

[0050] The pigment may be any pigment used in making decorativecoatings. These include opacifying pigments, such as titanium dioxideand zinc oxide, as well as tinting pigments such as carbon black, yellowoxides, brown oxides, tan oxides, raw and burnt sienna or umber,chromium oxide green, phthalocyanine green, phthalocyanine blue,ultramarine blue, cadmium pigments, and chromium pigments. The pigmentsinclude organic reds such as azo reds, quinacridone red and perylene redas well as organic yellows such as diarylide yellow. Mixed metal oxidepigments may be used. Filler pigments such as clay, silica, talc, mica,woloastonite wood flour, barium sulfate, calcium carbonate, aluminumsilicate, and the like can be added as well in conventional amountstraditionally used in coating and paint formulations.

[0051] The solvent may be an organic-based solvent, such as a ketone,ester, aliphatic compound, aromatic compound, alcohol, glycol, glycolether, etc. These include methylethyl ketone, methylisobutyl ketone,ethyl acetate, white spirits, alkanes, cycloalkanes, benzene,hydrocarbon substituted aromatic compounds (e.g., toluene, the xylenes,etc.), isoparaffinic solvents, and combinations of two or more thereof.Alternatively, water or a water-based solution may be used to form anaqueous emulsion with the binder or resin. Water-based solutions includewater-alcohol mixtures. The solvent or water is sufficiently volatile sothat when applied to a substrate, the solvent evaporates leaving behindthe binder or resin, pigment (if used), and any other additionalnon-volatile components.

[0052] Additional ingredients that may be used include wetting agents;plasticizers; suspension aids; thixotropic agents such as silica; waterrepellant additives such as polysiloxane compounds; fire retardantadditives; biocides; defoamers; and flow agents.

[0053] The pigment concentration for the liquid paint or coatingcomposition used to form the dry paint layers may range from about 10 toabout 30% by weight, and in one embodiment about 13 to about 27% byweight. The binder or resin concentration may range from about 20 toabout 40% by weight, and in one embodiment about 22 to about 37% byweight. The water or organic solvent concentration may range from about30 to about 70% by weight, and in one embodiment about 40 to about 60%by weight. The additional ingredients such as wetting agents, suspensionagents, etc., may have concentrations up to about 5% by weight. Thecoating or paint compositions used in making the dry paint layers mayhave a pigment to binder volume concentration in the range of about 5 toabout 35%, and in one embodiment 10 to about 30%.

[0054] The liquid paint or coating compositions used for making the drypaint layers may be blended using known techniques. The dry paint layermay comprise a single coat or multiple coats of paint and is in the formof a continuous layer, while the printed decorative layers mayindependently be in the form of continuous or discontinuous layers. Whenmultiple coats for the dry paint layer are used, each coat may have thesame or a different formulation. The print coats may have the same coloror a different color than the dry paint layer, or the print coats mayhave the same color, or they may have colors that are different fromeach other. The dry paint layer may be used to provide background colorwhile the print layers may be used to provide a desired pattern ordesign.

[0055] (a) Transparent Top Coat Layer

[0056] The transparent outer clear coat layer may comprise a singlecoating layer or multiple coats, and may comprise any of the resinousmaterials described above. When multiple coats are used, each coat mayhave the same or a different formulation. As mentioned previously, theouter clear coat layer may be solvent cast (aqueous or organic solventbased) or the outer clear coat layer may be extruded. The outer clearcoat layer, in one embodiment, provides enhanced scuff resistance, stainresistance and/or recoatability to the dry paint film layer or layersunderlying it. Enhanced recoatability facilitates the subsequentapplication of another dry paint film layer or printed decorative layerover it, or the application of conventional paint or decorative drypaint films.

[0057] (b) Reinforcing or Support Layer

[0058] The reinforcing or support layer may be formed from any of thebinder or resin materials described above. This layer may be formed froma solution or an emulsion and applied using any of the coatingtechniques described below. This layer also may be extruded. Thereinforcing layer may contain one or more of the above-describedpigments to enhance opacity of the finished laminate. The concentrationof pigment in the reinforcing layer, when used, may range up to about10% by weight, and in one embodiment about 6 to about 10% by weight.

[0059] The dry paint layers, outer clear coat layer or reinforcing layerindependently may contain inorganic fillers or other organic orinorganic additives to provide desired properties such as appearanceproperties (clear, opaque or colored films), durability and processingcharacteristics. Examples of useful materials include calcium carbonate,titanium dioxide, metal particles, fibers, flame retardants, antioxidantcompounds, heat stabilizers, light stabilizers, ultraviolet lightstabilizers, antiblocking agents, processing aids, and acid acceptors.

[0060] One or more of the dry paint layers, outer clear coat layer orreinforcing layer may contain a minor amount of an adhesive resin toenhance the adhesion of the dry paint layer to the outer clear coatlayer and/or the support layer. Also, or alternatively, tie coat layersof an adhesive resin can be used between the dry paint layers and eitherthe outer clear coat layer or the reinforcing layer. The adhesive resinfor the tie coat can be an acrylic resin adhesive, or it can be anethylene/vinyl acetate copolymer adhesive such as those available fromDuPont under the tradename Elvax. The adhesive resins available fromDuPont under the tradename Bynel also may be used.

[0061] In one embodiment, the dry paint layers, the outer clear coatlayer and/or the reinforcing layer are flexible, but non-stretchable andnon-elastic at room temperature.

[0062] Adhesive Layer

[0063] The dry adhesive layer may comprise a pressure-sensitive adhesive(PSA) which bonds the decorative laminate to a substrate surface, underapplied pressure, at room temperature. The adhesive layer may be acontinuous or discontinuous layer, and it may comprise one or a mixtureof two or more adhesives. The adhesive layer may be a patterned adhesivelayer with relatively strong adhesive tack level in some areas and arelatively weak adhesive in other areas.

[0064] In one embodiment, the adhesive layer is a repositionableadhesive, having a low initial tack that allows slight movement of thelaminate to allow positioning adjustments prior to forming a permanentbond. In one embodiment, the adhesive has a suppressed initial level oftack at room temperature that allows the laminate to adhere to asubstrate surface and be repositioned thereon followed by removal of thematte release liner from the decorative dry paint layer. The adhesivelayer undergoes a subsequent buildup of adhesion due to the passage oftime sufficient to permanently bond the dry paint layer to thesubstrate. In one embodiment, the adhesive layer is characterized byproducing only a limited amount of ooze beyond the borders of thelaminate when the laminate is applied to a substrate. In one embodiment,no ooze is produced.

[0065] In one embodiment of the invention described below, thepressure-sensitive adhesive comprises a cross-linked acrylic resinousmaterial, and more particularly, a cross-linked acrylic emulsion. Aparticularly useful adhesive material comprises an internallycross-linked acrylic emulsion. These pressure-sensitive adhesivematerials provide a useful combination of low tack, peel and flowproperties with a sufficient level of cohesive strength at a useful(thin) coat weight for providing the differential release propertiesdescribed below. High molecular weight acrylic adhesives and externallycross-linked acrylic adhesives also may be used to produce the desiredcombination of functional properties.

[0066] The adhesive may comprise a rubber based adhesive, acrylicadhesive, vinyl ether adhesive, silicone adhesive, or mixture of two ormore thereof. The adhesive may be applied to the laminate as a hot melt,solvent-based or water based adhesive. The adhesive materials that areuseful may contain as a major constituent an adhesive polymer such as anacrylic-type polymer; block copolymer; natural, reclaimed, orstyrene-butadiene rubber; tackified natural or synthetic rubber; acopolymer of ethylene and vinyl acetate; an ethylene-vinyl-acrylicterpolymer; polyisobutylene; or poly (vinyl ether). Other materials maybe included in the adhesive such as tackifying resins, plasticizers,antioxidants, fillers, and waxes.

[0067] A description of useful pressure-sensitive adhesives may be foundin Encyclopedia of Polymer Science and Engineering, Vol. 13.Wiley-Interscience Publishers (New York, 1988). Additional descriptionof useful pressure-sensitive adhesives may be found in Encyclopedia ofPolymer Science and Technology, Vol. 1, Interscience Publishers (NewYork, 1964).

[0068] Pressure-sensitive adhesives that may be used include the hotmelt pressure-sensitive adhesives available from H. B. Fuller Company,St. Paul, Minn. as HM-1597, HL-2207-X, HL-2115-X, HL-2193-X. Otheruseful pressure-sensitive adhesives include those available from CenturyAdhesives Corporation, Columbus, Ohio.

[0069] Conventional PSAs, including silicone-based PSAs, rubber-basedPSAs, and acrylic-based PSAs are useful. Another commercial example of ahot melt adhesive is H2187-01, sold by Ato Findley, Inc., of Wauwatusa,Wis. In addition, rubber based block copolymer PSAs described in U.S.Pat. No. 3,239,478 to Harlan also can be used. This patent isincorporated by reference for its disclosure of such hot melt adhesives.

[0070] The adhesive compositions may contain at least one solidtackifier resin component. A solid tackifier is defined herein as onehaving a softening point above 80° C. When the solid tackifier resincomponent is present, the adhesive compositions may comprise from about40% to about 80% by weight of a thermoplastic elastomer component, inone embodiment from about 20% to about 60% by weight, and in anotherembodiment from about 55% to about 65% by weight of a solid tackifierresin component. The solid tackifier reduces the modulus of the mixturesufficiently to build tack or adhesion. Also, solid tackifiers(particularly the higher molecular weight solid tackifiers (e.g., Mwgreater than about 2000) and those having a lower dispersity (Mw/Mn=lessthan about 3) may be less sensitive to migration into the polymer filmlayer. This is desirable since migration of tackifier into the filmlayer may cause dimensional instability.

[0071] The solid tackifier resins include hydrocarbon resins, rosin,hydrogenated rosin, rosin esters, polyterpene resins, and other resinswhich exhibit the proper balance of properties. A variety of usefulsolid tackifier resins are available commercially such as terpene resinswhich are sold under the trademark Zonatac by Arizona Chemical Company,petroleum hydrocarbons resins such as the resins sold under thetrademark Escorez by Exxon Chemical Company, or Wingtack 95, a synthetictackifier resin available from Goodyear, Akron, Ohio.

[0072] The modulus of adhesive mixtures to be coextruded also may belowered by the incorporation of liquid rubbers, i.e., liquid at roomtemperature. The liquid rubbers generally will have an Mw of at least5,000 and more often at least 20,000. Incorporation of liquid rubbers inamounts of less than 10%, and even less than 5% by weight based on theoverall weight of the adhesive formulation results in adhesives whichare coextrudable with the polymeric film materials. The incorporation ofa liquid rubber may produce an adhesive having increased tack andadhesion. Liquid block copolymers such as liquid styrene-isoprene blockcopolymers may be used. Other liquid rubbers which may be incorporatedinto the adhesive mixture include liquid styrene-butadiene rubbers,liquid butadiene rubbers, ethylene-propylene rubbers, etc.

[0073] The adhesive layer also may contain one or more pigments toenhance the opacity of the paint film layers overlying it and permit useof thinner paint film layers to achieve desired levels of opacity. Anyof the pigments identified above may be used. Examples include titaniumdioxide and carbon black. The pigment volume concentration may range upto about 10%, in one embodiment from about 5% to about 10%, and inanother embodiment from about 2% to about 8%.

[0074] The adhesive compositions also may include other materials suchas antioxidants, heat and light stabilizers, ultraviolet lightabsorbers, fillers, colorants, antiblocking agents, reinforcing agents,and processing aids.

[0075] The adhesive compositions may contain inorganic fillers and otherorganic and inorganic additives to provide desired properties. Examplesof useful fillers include calcium carbonate, titanium dioxide, metalparticles, and fibers.

[0076] Barrier Layer

[0077] The barrier layer may comprise any of the acrylate polymers orcopolymers described above, polyvinyl alcohol, copolymers derived fromethylene and vinyl acetate, and copolymers derived from ethylene, vinylacetate and polyvinyl alcohol. The barrier layer may comprise a polymerblend derived from polyvinyl alcohol, urethane, Cymel 385 (a product ofCytec identified as a melamine formaldehyde resin) and a polyaziridine(e.g., NeoCryl CX100 which is identified as trimethol-tris N (methylaziridinyl) proprionate and is available from Avecia Resins), the weightration of polyvinyl alcohol to urethane in one embodiment being about20:80. The following examples illustrate specific coating compositionswhich may be used in forming the barrier layer: Percent by WeightBarrier Layer No. 1 Elvacite 2042 (product of Ineos 20 identified as anethyl methacrylate copolymer) Tolune 48 Methyl ethyl ketone 32 BarrierLayer No. 2 Adcoat 61WG178 (product 55.55 of Rohm and Haas identified asa solution of acrylic polymer) Syloid 234 (product of Grace Davidson0.10 identified as synthetic amorphous silica) N-propanol 44.35 BarrierLayer No. 3 Adcoat 74.07 N-propanol 25.83 Syloid 234 0.10 Barrier LayerNo. 4 Adcoat 61WG178 55.55 N-propanol 44.35 Syloid 234 0.10 Desmodur CB75N (product of Bayer 0.44 identified as an oligomeric toluenediisocyanate) Barrier Layer No. 5 Adcoat 61WG178 74.07 N-propanol 25.83Syloid 234 0.10 Desmodur CB 75N 0.44 Barrier Layer No. 6 Adcoat 61WG17858.0 R-900 TiO₂ (product of DuPont identified 15.00 as rutile titaniumdioxide) N-propanol 24.0 Isobutanol 3.00 Barrier Layer No. 7 Adcoat61WG178 58.00 R-900 TiO₂ 15.00 N-propanol 24.00 Isobutanol 3.00 DesmodurCB 75N 0.88 Barrier Layer No. 8 Air Vol 523 (product of Air Products 5.0identified as polyvinyl alcohol) Water 47.5 Isopropanol 47.5

[0078] As mentioned previously, the substrate surface contacted by thedecorative laminate can comprise a painted surface having pigmentmaterials containing color constituents which can migrate into thedecorative film and through the adhesive layer to the color layer,causing discoloration. The barrier layer stops or retards thetransmission of undesired discoloration-causing pigments sufficient tomaintain discoloration or color shift of the color layer to within alevel which is essentially unnoticeable for a useful life of thedecorative film. Normal use conditions under which the decorative filmis applied and normally in use are defined as temperatures from about 4°C. (40° F.) to about 35° C. (90° F.), and more particularly, from about15° C. (60° F.) to about 27° C. (80° F.). To approximate the amount ofcolor shift that may occur during an estimated useful life of the filmunder normal use conditions, film samples are tested by acceleratedaging techniques and measured for color shift under those conditions.(Higher temperatures accelerate migration of discoloration colorconstituents.) In one embodiment, color shift is measured by comparingthe color of an interior latex test sample with an interior latex colorstandard and then subjecting the test sample to a 60°0 C. (140° F.)environment for approximately 400 hours (16 days). The test sample isthen measured for color shift and compared with the standard todetermine the amount of color shift. According to one test, color shiftis measured under ASTM 805 test procedures, and the unit of measure isC.I.E. color units on the Δb* (yellow/blue) scale, although other colorshift measurements can be used to determine whether color shift iswithin a specified range. These color shift measuring techniques areuseful in evaluating whether a color shift is acceptably low bymeasuring the color shift in a blue painted sample caused by migrationof yellow color constituents from mono azo pigments or dyes. In oneembodiment, the color shift is considered sufficiently low to be withinan acceptable range if testing at 60° C. for 400 hours produces a colorshift equal to or less than about 0.30 C.I.E. Δb* color units.

[0079] The barrier layer comprises a thin, flexible polymeric filmwhich, in one embodiment, can be cross-linked to enhance barrierproperties. One embodiment of the barrier layer comprises anon-pigmented acrylic resinous material which is cross-linked at across-linking density sufficient to retard transmission of mono azopigments to within the acceptable level. One embodiment of this barrierlayer comprises a relatively low molecular weight acrylic polymer whichis cross-linked with a melamine resin. A low molecular weight acrylicresin suitable for the barrier layer has a molecular weight below about100,000. One such cross-linked acrylic barrier layer (identified in moredetail in Example 9) is the acrylic polymer (Adcoat 61WG178 from Rohmand Haas) which has a molecular weight of about 50,000. Thecross-linking increases the molecular weight and raises the softeningpoint of the barrier coat and creates a network at the molecular levelthat retards transmission of the azo color constituents through thebarrier layer.

[0080] The use of a cross-linked polymeric material as a barrier coatcan be useful in producing the desired retardation, but in someinstances, the cross-linking of the resinous material can reduceadhesion to the PSA layer. In some instances, it is desirable to includea tie coat between the base coat and the PSA layer. One tie coat layerwhich has been shown to improve adhesion comprises a thin coating of amaterial similar to the pigmented base coat layer used in the decorativefilm. One example of such a tie coat is the plasticized vinyl tie coatshown in Example 9.

[0081] The PSA layer can be applied to the barrier coat by directcoating or casting of the PSA onto the previously formed barrier coat.Alternatively, the PSA can be separately cast on a temporary carrier andthen transfer-laminated from the carrier to the barrier coat.Experimental tests have shown that adhesion between the barrier coatingand the adhesive and the resistance to migration of color constituentsis better when the adhesive is coated directly onto the barrier coatingas opposed to transfer-lamination of the cast adhesive.

[0082] In another embodiment, the barrier layer can be made from athermoplastic (non-cross linked or lightly cross linked) polymericmaterial. One such material is the low molecular weight acrylic material(61WG178) described above. To increase the material's resistance tomigration of color constituents, a fine particulate filler material oradditive can be dispersed in the barrier material. The filler oradditive can have scavenging properties, or properties similar to alaking agent to which migrating pigments can attach, or the fillermaterial can physically retard transmission rate to a sufficiently lowlevel. Materials that have been found to reduce, capture, or stopmigration of mono azo pigments include fumed aluminum oxide, metalphosphate compounds and/or titanium dioxide, although other metal salts,or oxides, or metal compounds also can be used to produce similarresults. One metal compound useful in the barrier coat comprises analuminum zirconium phosphosilicate available as Xtain A from Halox.Tests have shown good color shift results for low molecular weightthermoplastic acrylic resinous barrier materials containing these typesof filler or additive materials. These materials also reduce color shiftin a cross-linked acrylic resinous barrier coat layer.

[0083] In one embodiment of the invention, in which the barrier coatcomprises a thermoplastic resinous material containing a dispersedfiller for retarding color transmission, adhesion to the PSA layer canbe enhanced by addition of a dispersed adhesion agent to the barriercoat. The low molecular weight thermoplastic acrylic barrier coat canhave adhesion properties enhanced by addition of polyvinyl pyrrolidonehomopolymer (PVP). This barrier coat produces good adhesion to PSAlayers which are either direct-coated or transfer-laminated to thebarrier coat. The PVP is compatible with the acrylic base polymermaterial and the solvents used in the system and also increases adhesionto the PSA layer. One source of the PVP is International SpecialtyProducts (ISP) identified as PVP K80.

[0084] Another embodiment of the barrier layer comprises a thermoplasticpolymeric material having a sufficiently high molecular weight to retardcolor transmission to within desirable limits. A suitable high molecularweight barrier material has a molecular weight in excess of 250,000. Onebarrier material comprises a high molecular weight acrylic resinousmaterial such as a polymethyl methacrylate (PMMA) having a molecularweight of about 350,000. This barrier material can produce theacceptable color shift results without addition of adhesion promoters oradditives and also can be used without an additional tie coat layer topromote adhesion to the PSA.

[0085] The barrier layer of this invention is applied at a sufficientlylow coat weight to produce a dry film thickness within a range of about0.05 to about 0.20 mil. The barrier coat is sufficiently thin so as tonot add significant thickness to the decorative portion (excluding therelease liner) of the multi-layer laminate. In one embodiment, filmthickness of the barrier layer is not more than about ten percent (10%)of the total thickness of the decorative portion of the film.

[0086] The barrier layer also is resistant to softening at elevatedtemperatures, and in one embodiment, the barrier layer has a glasstransition temperature (T_(g)) greater than about 60° C.

[0087] The addition of the barrier layer and the adjoining tie coatlayer (if used) does not impact the differential release properties ofthe decorative film. Adhesion of the barrier layer to the PSA layer issufficient to not appreciably reduce the peel force characteristics ofthe laminate in its self-wound form as described herein.

[0088] Matte Release Liner

[0089] The release liner may independently comprise paper, polymer film,or a combination thereof. The release liner, in one embodiment, isthermally stable, non-elastomeric and non-stretchable at roomtemperature.

[0090] Although paper of any weight may be used as a release liner,paper having weights in the range of from about 30 to about 120 poundsper ream are useful, and papers having weights in the range of fromabout 60 to about 100 pounds per ream are preferred. The term “ream” asused herein equals 3000 square feet.

[0091] Alternatively, the release liner may independently comprise apolymeric film, and examples of polymeric films include polyolefin,polyester, and combinations thereof. The release liner preferably may beformed from a flexible, foldable, heat-resistant, substantiallyinelastic, self-supporting temporary carrier film or casting sheet as isknown in the art of dry paint transfer films. The release liner ispreferably an oriented polyester film such as polyethylene terephthalate(PET) available as Mylar, a trademark of DuPont, or Hoechst CelaneseHostaphan 2000 polyester film, for example.

[0092] The release liner provides structural integrity to the laminateuntil the liner is removed upon application of the laminate to asubstrate surface.

[0093] The matte release coat layer may comprise any of the aboveidentified binders or resins which provide a level of tack or adherencebetween the release coat layer and the decorative dry paint layer, whichmay comprise either the color coat layer, the outer clear coat layer, orthe decorative print layer. The tack level of the matte release coatlayer is sufficient to prevent separation of the release coat layer fromthe adhered dry paint layer during the process of forming the dry painttransfer laminate and during normal handling of the laminate, includingforming it in its self-wound orientation, unwinding it, and applying itto the substrate surface. The matte release coat also continues to havesufficient release properties to facilitate separation between therelease coat layer and the adhered dry paint layer after having appliedthe laminate to the substrate.

[0094] The matte release coat formulation comprises a coating which canbe applied to the release liner by conventional casting techniques suchas gravine printing. The preferred coating composition is athermosetting resinous material which, when exposed to heat for dryingit, also cross links and permanently bonds as a surface film adhered tothe release liner. The solids contained in the matte release coatpreferably include, as a principal component, one or more crosslinkingagents to provide good adhesion of the dried crosslinked coating to apolyester carrier film. In one embodiment, the matte release coatformulation includes a primary crosslinking resin such as a melamineresin that controls crosslinking and produces adhesion to the polyestercarrier film. A presently preferred crosslinking resin is hexamethoxymethyl resin such as Cymel 303. A suitable primary functional resin is avinyl resin such as a medium molecular weight vinyl chloride-vinylacetate resin known as VAGH. The vinyl resin can be present in an amountup to about 20% of the total solids in the matte release coat. Inaddition, the matte release coat can include a secondary functionalresin to improve release of the top surface of the decorative dry paintlayer from the matte release coat. In one embodiment, the secondaryfunctional resin can be an acrylic-modified alkyd resin such as theresin known as Chempol 13 1501 or Lankyd 13-1245. This secondaryfunctional resin comprises from about one percent to about 16% of thetotal solids, by weight, of the matte release coat. The matte releasecoat further includes a suitable catalyst for accelerating thecrosslinking process, typically comprising from about one percent toabout eight percent of the total solids in the matte release coat, byweight.

[0095] The resinous components of the matte release coat composition arecombined with suitable solvents. In one embodiment, the resins are mixedwith a primary resin solvent such as methyl isobutyl ketone (MIBK) whichcomprises from about 65% to about 85% of the total solvent in theformulation. A secondary resin solvent, such as isopropyl alcohol(IPOH), is useful in retarding crosslinking of resins in solution. Thesecondary resin solvent preferably comprises from about 5% to about 20%of the total solvent.

[0096] The matte release coat formulation is prepared by dissolving theprimary functional resin in the primary and secondary resin solvents bymixing and then adding the secondary functional resin together with aprimary matting agent, preferably in the form of a filler comprising afine particulate inert inorganic material. In one embodiment, the fillercomprises aluminum silicate with an average particle size of about 4.8microns. In another embodiment, the filler can comprise talc. The fillercontained in the formulation comprises up to about 50% of the totalsolids in the matte release coat. In one embodiment, the talc fillermaterial comprises from about 40% to about 50% of the total solidscontained in the matte release coat. The fine particulate filler isthoroughly dispersed in the resin and resin solvent blend, preferablyunder elevated temperatures from about 100° F. to about 120° F.

[0097] In use, when the matte release layer dries and cross links, itforms a chemical matte coating on the surface of the carrier sheet. Thematte surface is controlled by the amount and particle size of thefiller. The fine particles project through the dried exterior surface ofthe matte release coat to form, on a microscopic scale, a surface with amicroroughness that transfers a replicated microroughness to the exposedsurface of the dried outer clear coat or dry paint layer. This produceslight scattering, resulting in a flat or low surface gloss matte finishon the top surface of the decorative dry paint layer.

[0098] In one embodiment a matte release coat formulation useful forthis invention contains no significant amount of a silicone-basedrelease material and/or a wax-based component. Such materials may beuseful in providing release properties at high temperatures; but thematte release coat of this invention, in one embodiment, comprises aformulation that, in the absence of a silicone-based release material ora wax-based component, provides a useful combination of room temperaturerelease, adherence of the release liner to the dry paint layer, andtransfer of the matte surface to the exposed surface of the dry paintlayer. Stated another way, the matte release coat has a hardened stateat room temperature and is made from a resinous material that contains(1) a surfacing component that forms a matte release surface, (2) anadhesion component for releasably adhering the matte release surface tothe dry paint layer, and (3) a release component that releases the matterelease surface from contact with the dry paint layer at roomtemperature to transfer the matte surface finish from the matte releasesurface to the exposed surface of the dry paint layer.

[0099] In one embodiment, the matte release coat comprises, on a solidsbasis, from about 10% to about 30% by weight alkyd resin; from about 10%to about 30% by weight vinyl resin; from about 20% to about 35% byweight melamine crosslinking resin; and from about 5% to about 10%catalyst. The balance of the solids comprises the fine particulatefiller, e.g. talc, as described previously.

[0100] In one embodiment, the weight ratio of particulates to resin orbinder may range up to about 1.1:1, in one embodiment from about 0.7:1to about 1.1:1, in another embodiment from about 0.7:1 to about 0.9:1,and in a further embodiment from about 0.9:1 to about 1.1:1.

[0101] The gloss transferred to the outer surface of the dry paint layercan be controlled by a combination of release coat formulations and thecomposition of the outer surface layer of dry paint in contact with therelease coat. In one embodiment, an 85° gloss of less than about 10gloss units can be transferred to dry paint films having a monocoat orbase coat/clear coat finish comprised of urethane, acrylic and/or vinylresinous paint layers. The preferred release coat comprises anacrylic/vinyl blend containing a micro-particle filler. In anotherembodiment, 85° gloss measurements of less than about 35 gloss units canbe transferred to dry paint films having a monocoat or base coat/clearcoat finish comprised of urethane, acrylic and/or vinyl resinous paintlayers. The preferred release coat comprises an acrylic modified alkydresin and/or vinyl resins containing dispersed microparticles.

[0102] The carrier film or release liner is typically contained on asupply roll from which the carrier is unwound and passed to a gravureprint station where the matte release coat is coated onto the releaseliner. The release liner containing the matte release coat is thenpassed through a drying oven operated at a temperature from about 325°F. to about 350° F., sufficient for drying and crosslinking the matterelease coat. In the first stage drying oven, the matte release coat issufficiently cross-linked to permanently bond it to the carrier sheet.Preferably, the matte release coat is coated and dried to a coat weight(dry) from about 3 to about 6 gsm.

[0103] The adhesive release coat layer may comprise any release coatingcomposition known in the art. Silicone release coating compositions maybe used. The silicone release coating compositions typically comprisepolyorganosiloxanes such as polydimethylsiloxanes. The silicone releasecoating composition used in this invention may be room temperaturecured, thermally cured, or radiation cured. Generally, the roomtemperature and thermally curable compositions comprise at least onepolyorganosiloxane and at least one catalyst (or curing agent) for suchpolyorganosiloxane(s). These compositions may also contain at least onecure accelerator and/or adhesivity promoter.

[0104] Each of the layers in the multi-layer laminate may beindependently applied and dried and/or cured using known techniques. Theapplication techniques include gravure, reverse gravure, offset gravure,roll coating, brushing, knife-over roll, metering rod, reverse rollcoating, doctor knife, dipping, die coating, slot die coating, spraying,curtain coating, slide coating, slide curtain coating, extrusion,co-extrusion, flexographic, letter press, rotary screen, and flatscreen. In one embodiment, the pressure sensitive adhesive layer may beapplied using transfer lamination. The decorative print layers may beapplied using known printing techniques including gravure, flexographic,silk screen, and ink jet printing. The applied layers may be driedand/or cured by exposure to heat or to known forms of ionizing oractinic non-ionizing radiation. Drying or curing temperatures that maybe used may range from about 115° C. to about 160° C., and in oneembodiment about 140° C. to about 150° C. Useful types of radiationinclude ultraviolet light and electron beam. The equipment forgenerating these forms of thermal or radiation drying and/or curing arewell known to those skilled in the art.

[0105] Various layers of the multi-layer laminate also can be formed byextrusion and co-extrusion techniques identified above and described inmore detail in U.S. application Ser. No. 457,826 identified above andincorporated herein by reference. The dry paint layer or the supportlayer may be coextruded with the adhesive layer using separate extrudersas illustrated in FIG. 8 or a dual die extruder as illustrated in FIG.9. Referring to FIG. 8, release liner 70 is uncoiled from a roll 72 andadvanced past an extrusion die 74 where it is coated with an adhesivelayer 76, and then past an extrusion die 78 where a reinforcing orsupport layer 79 is coated onto the adhesive layer 76. The resultingco-extrudate is collected on a take-up roll 80. Referring to FIG. 9, therelease liner 70 is advanced past a dual extrusion die 82 whichsimultaneously coats the release liner 70 with a coextruded adhesivelayer 84 and support layer 86. The resulting co-extrudate is collectedon a take-up roll 88.

[0106] The dry paint transfer laminate illustrated in FIG. 1 may be madeby applying the adhesive release coat to the lower surface of therelease liner using one of the foregoing application techniques and thencuring the release coat. The coat weight for the adhesive release coatlayer may be in the range from about 0.1 to about one gram per squaremeter (gsm), and in one embodiment from about 0.25 to about 0.35 gsm.The matte release coat layer is then applied to the upper surface ofrelease liner using one of the above described application techniques(e.g., gravure) and then dried or cured. The coat weight for the matterelease coat may be in the range from about 2.5 to about 6.5 gsm, and inone embodiment, from about 4.5 to about 5.5 gsm. The liquid paint orcoating composition for forming the pigmented dry paint layer is thenapplied to the surface of the matte release coat layer using one of theabove described application techniques (e.g., reverse roll or slot die)and then dried or cured. The coat weight for the pigmented dry paintlayer may range from about 20 to about 60 gsm, and in one embodimentabout 30 to about 40 gsm. One or more coats may be applied. Thepressure-sensitive adhesive layer is then applied to the upper surfaceof dry paint layer using one of the above indicated applicationtechniques (e.g., slot die) and then dried or cured. The pressuresensitive adhesive may be applied using coating techniques or transferlamination. The coat weight for the pressure sensitive adhesive layermay range from about 10 to about 30 gsm, and in one embodiment about 11to about 17 gsm. The dry paint transfer laminate 20 may then be woundinto roll form as illustrated in FIG. 2.

[0107] The dry paint transfer laminate illustrated in FIG. 3 may be madeusing the same procedure as the laminate 20 of FIG. 1, except that thetransparent outer clear coat layer is applied to the matte release coatlayer and then dried or cured prior to application of the pigmented drypaint film layer. The dry paint layer is then applied to the surface ofthe clear coat layer. The clear coat layer may be applied using one ofthe foregoing application techniques (e.g., gravure). The coat weightfor the clear coat layer may range from about one to about 5 gsm, and inone embodiment about 2.5 to about 3.5 gsm. One or more coats may beapplied. The dry paint transfer laminate may then be wound into a rollas illustrated in FIG. 2.

[0108] The dry paint transfer laminate illustrated in FIG. 4 may be madeusing the same procedure used as the laminate 20, except that the liquidpaint composition for forming the printed decorative layer is applied tothe surface of the transparent film layer and then cured prior toapplication of the dry paint film layer. The dry paint film layer isthen applied to the surface of the printed decorative layer. The printeddecorative layer may be applied using any of the foregoing printingtechniques (e.g., gravure, flexographic, silk screen, or ink jet). Thecoat weight for the printed decorative layer may range from about 0.3 toabout 2 gsm, and in one embodiment about 0.3 to about 0.7 gsm. The drypaint transfer laminate may then be wound into a roll as illustrated inFIG. 2.

[0109] The dry paint transfer laminate illustrated in FIG. 5 may be madeusing the same procedure as the laminate of FIG. 4, except that theliquid paint composition for forming the second printed decorative layeris applied to the surface of the transparent film layer and then driedor cured prior to the application of the first printed decorative layer.The second printed decorative layer may be applied using any of theforegoing printing techniques (e.g., gravure, flexographic, silk screen,ink jet). The coat weight for the second printed decorative layer mayrange from about 0.3 to about 2 gsm, and in one embodiment about 0.3 toabout 0.7 gsm. The dry paint transfer laminate may then be wound into aroll as illustrated in FIG. 2.

[0110] The dry paint transfer laminate illustrated in FIG. 6 may be madeusing the same procedure used for making the laminate 20 illustrated inFIG. 1, except that the reinforcing layer is adhered to the dry paintlayer. The reinforcing layer may be coextruded with the adhesive layerand then the dry paint film layer may be coated (e.g., gravure) onto thereinforcing layer. The dry paint transfer laminate may then be woundinto a roll as illustrated in FIG. 2.

[0111] The dry paint transfer laminate illustrated in FIG. 7 may be madeusing the same procedure used for making the laminate 20 illustrated inFIG. 1, except that the barrier layer is coated on the dry painttransfer layer. The dry paint transfer laminate may then be wound into aroll as illustrated in FIG. 2.

[0112] The dry paint transfer laminate may be made in a singleproduction line or in multiple production lines or multiple productionfacilities. With multiple production lines or facilities, part of thelaminate may be produced as a roll laminate, dried or cured, rolled up,transferred to the next production line or facility, unrolled, andfurther treated with the application of additional layers. For example,the dry paint layer and the adhesive layer may be formed in multiplelines, or they may be formed in sequence in a single production line, orthey may be simultaneously formed such as by coextrusion or multi-diecoating methods.

[0113] The dry paint transfer laminate 20 may be used by unrolling thelaminate from the roll illustrated in FIG. 2, and simultaneouslyapplying the laminate to the substrate surface to be covered. Thesubstrate may comprise any flat surface. The flat surface may comprisewall board, plastic sheet, metal sheet, composites, and the like. Thesubstrate may comprise an interior (i.e., indoor) surface or an exterior(i.e., outdoor) surface. The laminate may be applied to a paintedsurface having various surface finishes, from flat, semi-gloss toglossy. The laminate is placed over the substrate with the adhesivelayer in contact with the substrate. Pressure is applied, withrepositioning if necessary, until the laminate is adhered to thesurface. The release liner is then peeled off the front face of thedecorative laminate, leaving the dry paint film layer adhered to thesubstrate by the adhesive layer. The dry paint transfer laminates shownin FIGS. 3 through 7 and in FIG. 10 also may be applied to a substratesurface in the same manner as the laminate 20.

[0114] Differential Release System

[0115] In one embodiment of the invention, the release properties of thelaminate are controlled so that, in the embodiments illustrated in FIGS.1-7 and FIG. 10, the release force required to separate the matterelease coat layer from the dry paint layer (which may comprise thetransparent layer, the color layer, or printed decorative layer) isgreater than the release force required to separate the adhesive releasecoat layer from the pressure-sensitive adhesive layer.

[0116] In one embodiment, the carrier release force required to separatethe matte release coat layer from the dry paint layer (i.e., the colorlayer, the clear coat layer, or the printed decorative layer) may begenerally in the range from about 20 to about 180 grams per two inches(g/2 in), in one embodiment from 30 to about 150 g/2 in, and in anotherembodiment 40 to about 120 g/2 in. In other embodiments the releaseforce range may be from 50 to about 100 g/2 in, from 50 to about 90 g/2in, from about 70 to about 90 g/2 in, and from about 50 to about 65 g/2in.

[0117] In one embodiment, the unwind release force required to separatethe adhesive release coat layer from the pressure-sensitive adhesivelayer is generally in the range from about 10 to about 150 g/2 in, inone embodiment from about 20 to about 150 g/2 in, in another embodimentabout 20 to about 90 g/2 in, and in other embodiments from about 30 toabout 150 g/2 in, about 30 to about 100 g/2 in, and about 30 to about 70g/2 in.

[0118] The test method for determining these release forces involvesmeasuring the force required to separate a two-inch wide release coatedliner from the dry paint layer or from an adhesive coated substrate,with the release coated liner extending at an angle of 90° relative tothe layer or substrate and being pulled at a rate of 300 inches perminute. The test is conducted at room temperature.

[0119] According to one embodiment of the invention, the decorative filmcontains a differential release system which enables the film to beunrolled from its self-wound form with the release liner maintainingcontinuous contact with the dry paint layer. As the decorative film isunrolled, the silicone-coated outer surface of the release linerpreferentially releases from contact with the PSA side of the film whilethe matte release coat side of the release liner maintains constantcontact with the dry paint layer. This contact of the release liner withthe dry paint layer is maintained throughout unwinding, application tothe substrate surface, and any repositioning of the decorative film onthe surface, until the release liner is ready to be peeled away from thedecorative paint layer. The differential release system is adapted tomaintain such preferential contact between the release liner and the drypaint layer because the dry paint layer is non-self-supporting, i.e., ithas no structural integrity in and of itself, and therefore relies uponits contact with the release liner to provide the necessary structuralsupport during unrolling, handling and repositioning, for example.

[0120] As mentioned previously, the release force between the releaseliner and the matte release layer (carrier release force) exceeds therelease force between the silicone-coated side of the releaser liner andthe PSA (unwind release force). Tests have shown that this “forcedifferential” is dependent upon the rate or speed at which the materialsat each interface are peeled away from each other. Inasmuch as theself-wound film, in use, may be unwound at different speeds, anobjective of the differential release system is to ensure that thecarrier release force exceeds the unwind release force over a wide rangeof release rates that are normally encountered during use. Generallyspeaking, this force differential is maintained over a wide range ofspeeds. During use, slow rates are encountered when unwinding a new rollor during the initial start of a roll on the surface. Medium to fastrates are encountered when the strip continues down the surface. In oneembodiment, the force differential is maintained for a range of speedsup to about 300 inches per minute for a 2 inch wide strip. In anotherembodiment, this force differential is maintained up to a speed of atleast 600 inches per minute for a 2 inch wide strip.

[0121] The force needed to remove the PSA from the silicone side of theliner also should be less than the force needed to peel the carrier offthe dry paint side in order to prevent peeling the carrier duringslitting or unwinding, in addition to avoiding peeling of the carrierduring unrolling, application to a surface, and repositioning on thesurface. Unwind speeds in excess of 600 inches per minute may beencountered when cutting the film to individual roll sizes, but testshave shown that, in one embodiment, at such high speeds an undesiredunwind response is not produced even when unwind release forces exceedcarrier release force.

[0122] Such differential release forces can be measured, as describedpreviously, by separating the liner from the matte release layer or thePSA layer in a two-inch wide strip at an angle of 90° pulled at a rateof 300 inches per minute with the tests conducted at room temperature.In one embodiment, the carrier release force is maintained higher thanthe unwind release force for release rates from about 6 inches perminute up to at least about 300 inches per minute. In anotherembodiment, the carrier release force is maintained within a range fromabout 45 to about 65 grams/2 inches over a wide range of release ratesfrom about 6 inches per minute up to at least about 300 inches perminute. A corresponding unwind release force is maintained within arange from about 20 to about 40 grams/2 inches, over a range of linerrelease rates from about 12 to about 60 inches per minute.

[0123] Tests have shown that carrier release forces are maintained at arelatively uniform level across a wide range of release rates, whereasunwind release forces tend to increase as release rates increase and caneventually exceed the carrier release forces above certain higherrelease rate levels. However, tests have shown that for release ratesabove about 300 inches per minute, an unwind release force in excess ofthe carrier release force does not negatively impact premature releaseof the release liner from the matte release layer during normal useconditions of the self-wound decorative film.

[0124] The composition of the PSA is coordinated with the composition ofthe dry paint layer in order to produce the desired differential releaseproperties. The particular formulation used for the PSA can affectunwind release response. In addition, the composition of the dry paintlayer which comes into contact with the matte release layer can affectrelease properties. In one embodiment, a relatively low unwind releaseforce can be desirable if the carrier release force is relativelyhigher. However, there are limitations on the absolute magnitude of thecarrier release force. Producing a substantially higher carrier releaseforce compared to the lower unwind release force can maintain desiredcontact between the carrier and dry paint film during unwinding andapplication to a substrate surface; but if the carrier release force istoo high, there may be difficulties in producing a proper release of therelease liner from the dry paint layer after the PSA side of thelaminate has been affixed to the substrate surface. If the carrierrelease force is too high, the user may experience difficulty ininitially peeling the liner from the paint film; or removing the releaseliner may overcome the bond between the dry paint layer and thesubstrate and result in peeling the dry paint layer from the surface.

[0125] Therefore, another objective of the invention is to produce adifferential release system in which the carrier release force is higherthan the unwind release force over a broad range of release rates, butthe carrier release force level is maintained below a certain maximumforce level. In one embodiment, a preferred dry paint layer comprises atransparent outer clear coat layer as described in Examples 7 and 9, inwhich the outer layer comprises a solvent-cast acrylic resinousmaterial. This top coat material provides benefits of abrasion and stainresistance and repaintability in the finished film in addition to auseful carrier release force level when the matte release liner ispeeled from the outer layer. The composition of the matte release coatin this embodiment comprises the alkyd/vinyl/melamine resinouscomposition of Examples 7 or 9, and the composition of the PSA comprisesthe adhesive formulation of Examples 7 or 9. In this embodiment, thecarrier release force when peeled from the acrylic-based paint layer ismaintained within a range of about 45 to about 65 grams per 2 inches.Corresponding unwind release force is maintained within a range of about20 to about 40 grams per 2 inches, over a range of liner release ratesfrom about 12 to at least about 60 inches per minute. It has beenobserved that the lower carrier release force level associated with theacrylic-based outer clear coat layer, i.e., below about 65 grams per 2inches, provides sufficiently low carrier release properties to enableusers to easily remove the release liner over a wide range of useconditions and carrier release rates.

[0126] By lowering the unwind release force response, the carrierrelease force then can be lowered to a more desirable level as mentionedpreviously. The PSA used in the present invention is preferably aninternally cross-linked pressure-sensitive adhesive which lowers peeland tack levels. In one embodiment, the internally cross-linkedacrylate-based copolymer emulsion PSA of Example 9, for instance,produces unwind release levels that are sufficiently low to allow use ofmatte release coatings that produce carrier release responses at themore desirable lower levels as described previously. Use of anon-crosslinked (or lightly crosslinked) pressure-sensitive adhesive,which is softer, can have undesirable edge ooze characteristics duringuse; but in addition, it can produce higher peel and tack levels thatundesirably increase the unwind release force in a direction toward thecarrier release force.

[0127] The matte release coat composition also can control the carrierrelease force level. In the matte release coat formulation of Examples 7and 9, the melamine crosslinking agent can be used to control thecarrier release force level. The content of the alkyd resin and thelower molecular weight vinyl resin also can be controlled to lowerrelease force. A useful combination of these components can producedesired room temperature adhesion to the release liner and release forceresponse when peeling the release liner from the dry paint layersurface. The release coat composition also controls uniformity of andgloss level of the transferred matte surface.

[0128] As mentioned, the tack or peel level of the PSA also iscontrolled with respect to the surface to which the laminate is affixed.That is, the PSA in its dry form must have a low unwind release forcefrom the silicone-coated release liner but also must have a sufficientlevel of tack to properly adhere to a substrate surface as well asproviding sufficient repositionability.

[0129] A pressure sensitive adhesive useful for this invention ischaracterized by relatively low tack and peel force levels andrelatively low room temperature flow properties. Such adhesives, if theyare too soft, can undesirably increase unwind force and can adverselyaffect repositioning of the paint film. Acrylic emulsion PSAs areparticularly useful when such PSAs have a level of crosslinking thatproduces an adhesive material with a relatively high cohesive strengththat yields a desirable combination of low tack, peel and flowproperties. Examples of useful PSAs in which the level of crosslinkingcan be appropriately adjusted include acrylic emulsion PSAs such as purepolymer (butyl acrylate or 2-ethyl hexyl acrylate or 2-ethyl hexylacrylate/butyl acrylate) PSAs or similar pigmented polymer and copolymermaterials.

[0130] A particularly useful PSA for this invention is an internallycross-linked acrylic emulsion PSA such as a non-tackified cross-linkedcopolymer emulsion of butyl acrylate and 2-ethyl hexyl acrylate. Thisparticular adhesive contains a crosslinking agent which controls thelevel of crosslinking and produces a desirable combination of low tack,peel and flow and relatively high cohesive strength at a useful low coatweight. This adhesive is available from Avery Dennison Corporation asproduct no. S-3506, or in its pigmented form as product no. S-3526.

[0131] Other multi-functional acrylic-based polymer and copolymermaterials can be used to produce similar adhesive properties in theircross-linked form. In addition, other suitable pressure-sensitiveadhesives for this invention can comprise high molecular weight acrylicemulsion adhesives. Such high molecular weight adhesives can behave in amanner similar to the cross-linked adhesives in producing low tack, peeland flow characteristics at sufficiently high cohesive strength.Exterior crosslinking agents also can be used to provide the desiredlevel of crosslinking in such pressure sensitive adhesives materials.

[0132] Another useful adhesive is a high molecular weight cross-linkedacrylic emulsion adhesive (butyl acrylate/2-ethyl hexyl acrylate)available from Avery Dennison as product no. S-3000.

[0133] As mentioned previously, the PSA useful for this invention can becharacterized, in part, as an adhesive that produces an unwind releaseforce which is lower than the carrier release force, when releasing fromcontact with a silicone-coated release liner. The PSA also can becharacterized, in part, by its level of adhesion to a substrate such asflat paint, glossy paint, primed drywall or stainless steel, forexample. In one embodiment, the PSA formulation can be controlled toproduce a low level of tack characterized by a looptack value within therange of about 0.8 to about 2.4 lbs/in, in which the adhesive ismeasured for adhesion to stainless steel and laminated to a 2 mil PETfacestock, at a standard coat weight of 15 gsm.

[0134] In another embodiment, the PSA formulation can be controlled toproduce a low level of 90° peel force adhesion, characterized by 15minute peel adhesion to stainless steel in the range of 0.80 to 1.5lbs/in for 2 mil PET; or 15 minute peel adhesion to flat paintedsurfaces of 0.05 to 0.30 lbs/in, or 15 minute peel adhesion to glossypainted surfaces of 0.20 to 0.40 lbs/in in which the adhesive islaminated to the dry paint transfer film with the release liner carrier.

[0135] In another embodiment, the PSA can be adjusted to produce a lowpeel force characterized by 90° peel adhesion values at 24 hours asfollows: dry wall—0.30 to 0.50 lbs/in; flat paint—0.40 to 0.65 lbs/in;and glossy paint—0.60 to 0.90 lbs/in.

[0136] The PSA also can be characterized by its desired low flowproperties at room temperature. Such characteristics can be measured byits WPI (plasticity) value which in one embodiment has a WPI value fromabout 3.2 to about 3.8 mm.

[0137] The desired PSA also has a sufficient level of cohesive strengththat enables the adhesive to permanently bond the paint film to the wallin the absence of a high level of tack. The level of crosslinking caneffect such a cohesive strength, and in one embodiment, the cohesivestrength is measured by a shear value of greater than 1,000 minutes (500g ¼ sq. in., 20 minute dwell, 14-16 gsm coat weight direct coated on 2mil PET dried at 120° C. for 5 minutes).

EXAMPLES 1 and 2

[0138] A polyethylene terephthalate (PET) release liner is coated on oneside with a silicone release coating corresponding to the adhesiverelease coating layer. The thickness of the release coated liner is 0.92mil, also known as Mitsubishi 92 gauge SLK.

[0139] A matte release coat is applied to the other side of the releaseliner using gravure at a coat weight of 6.5-7.75 gsm. The formulationfor the matte release coat is as follows: 26 parts by weightmethylisobutyl ketone, 6 parts by weight isopropanol, 34.8 parts byweight Lankyd 13-1425 (a product supplied by Akzo Resins identified asan acrylic modified alkyd), 2.6 parts by weight Elvacite 2042 (a productsupplied by Lucite International identified as a polyethyl methacrylatepolymer), 30 parts by weight Microtalc MP 15-38 (a product supplied byBarretts Minerals identified as a talc extender pigment), 2.5 parts byweight Cycat 4040 (a product supplied by Cytec identified as paratoluenesulfonic acid), and 8.7 parts by weight Cymel 303 (a product supplied byCytec identified as a melamine resin). The matte release coat is driedusing forced hot air at a temperature of 149° C. which crosslinks theresin and bonds the matte silicone coat to the polyester carrier. Thetalc particles project from the surface of the dried matte release coatto form a microroughened surface.

[0140] A transparent clear coat layer is applied to the matte releasecoat using gravure at a coat weight of 2.7-2.9 gsm and dried usingforced hot air at a temperature of 120° C. The formulation for the clearcoat layer is as follows: 46.7% by weight methyl ethyl ketone, 31.3% byweight toluene, 11% by weight VYNS (a product of Union Carbideidentified as a vinyl chloride/vinyl acetate copolymer containing 5-20%by weight vinyl acetate), and 11% by weight Vitel 2200B (a product ofBostic identified as a polyester copolymer).

[0141] The following paint compositions are used to form a dry paintlayer on the clear coat layer, one for Example 1 and the other forExample 2. The dry paint layer of Example 1 has a deep brown tone, whilethe dry paint layer of Example 2 has an orange pastel tone. In thefollowing table, all numerical values are in parts by weight. ComponentExample 1 Example 2 Methylethyl ketone 66.7 66.7 Toluene 33.3 33.3 VYHH(product of Union Carbide 50.05 30.55 identified as a vinylchloride/vinyl acetate copolymer) Edenol 9790 (a product of Cognis 24.6515.05 identified as a polyester plasticizer) Yellow pigment 42 (ironoxide) 17.8 2.3 Orange pigment 36 (monoazo 2.5 0.38 benzimidazoline)Black 7 (carbon black) 0.1 0.02 White 6 (titanium dioxide) 4.9 51.7

[0142] The pigment-to-binder volume ratio for Example 1 is 10%, and forExample 2 the ratio is 27%. The above paint formulations are applied tothe clear coat layer using a reverse roll coater and are dried at atemperature of 135° C. to drive off the solvents. The dry film thicknessof each of the dry paint layers is 0.7 mil.

[0143] A pigmented pressure sensitive adhesive is then applied to thedry paint layer at a coat weight of 14-20 gsm using transfer laminationto provide an adhesive layer corresponding to pressure sensitiveadhesive layer 120. The adhesive is an ethyl hexyl acrylate based PSAavailable from Avery Dennison Corporation under product no. S-692N andthe formulation for the pressure sensitive adhesive is as follows:70-90% by weight 2-ethyl hexyl acrylate, 1-10% by weight acrylic acid,10-20% by weight methyl acrylate, 3.7% UCD 1106E (a product of Rohm andHaas identified as a titanium dioxide dispersion concentrate), and 0.3%by weight of UCD 1507E (a product of Rohm and Haas identified as acarbon black dispersion concentrate).

EXAMPLE 3

[0144] The procedure used for Examples 1 and 2 is repeated except thatthe following liquid paint composition is used to form the dry paintlayer. In the following table, all numerical values are in parts byweight. Component Parts Methylethyl ketone 29.6 Toluene 19.5 Vitel 2200B 11.6 Vitel 2650 (product of Bostic identified 11.5 as a polyestercopolymer) R-900 (product of DuPont identified as 27.5 titanium dioxide)955-39230 (product of Gibraltar Chemical  0.2 Works identified asshading black) 99-34520 (product of Gibraltar Chemical  0.1 Worksidentified as phthalo blue GS) 955-37470 (product of Gibraltar Chemicaltint Works identified as carbazole violet)

[0145] The foregoing paint composition has a light blue color. The dryfilm thickness of the dry paint film layer is 0.6-0.8 mil.

EXAMPLE 4

[0146] A PET release liner is coated on one side with a silicone releasecoating corresponding to the adhesive release coat layer. The thicknessof the release coated liner is 0.92 mil.

[0147] A matte release coat layer is applied to the other side of therelease liner using gravure at a coat weight of 4.4-4.6 gsm. Theformulation for the matte release coat is as follows: 50.54 parts byweight methylisobutyl ketone, 7.84 parts by weight isopropanol, 8.93parts by weight Lankyd 13-1425, 10.68 parts by weight VAGH (product ofUnion Carbide identified as hydroxy modified polyvinylchloride/polyvinyl acetate copolymer), 22 parts by weight Microtalc MP15-38, 2 parts by weight Cycat 4040, and 6.8 parts by weight Cymel 303.The matte release coat is dried using forced hot air at a temperature of149° C.

[0148] A first coat of a transparent outer clear coat layer is appliedto the matte release coat using gravure at a coat weight of 1.3-2 gsmand dried using forced hot air at a temperature of 120° C. The dry filmthickness is 0.05-0.1 mil. The formulation for this first clear coatlayer is as follows: 41.5% by weight methyl ethyl ketone, 41.5% byweight methyl isobutyl ketone, and 17% by weight Elvacite 2042 (aproduct of Lucite International identified as a polymethylmethacrylate).

[0149] A second coat of a clear coat layer is applied over the firsttransparent layer using gravure at a coat weight of 1.0-1.5 gsm anddried using forced hot air at a temperature of 120° C. The dry filmthickness is 0.03-0.1 mil. The formulation for this second transparentfilm layer coat is as follows: 41.5% by weight methyl ethyl ketone,41.5% by weight methyl isobutyl ketone, and 17% by weight VYHH (aproduct of Union Carbide identified as a vinyl chloride/vinyl acetatecopolymer containing 5-20% by weight vinyl acetate).

[0150] A decorative print layer is printed over the second transparentclear coat layer at a coat weight of 3.0-3.2 gsm and dried in hot air ata temperature of 120° C. The paint composition for this decorative printlayer has the following formulation (all numerical values are in partsby weight): Component Parts Methylethyl ketone 42.6 Methyl isobutylketone 38.7 VYHH 15.86 DP 80110 (product of Gibraltar Chemical 2.1 Worksidentified as containing methylethyl ketone, toluene, carbon black andacrylic polymer) DP 36640 (product of Gibraltar Chemical 0.22 Worksidentified as containing methyl ethyl ketone, toluene, quinacridone red,and acrylic polymer) I8977 (product of Gibraltar Chemical 0.10 Worksidentified as containing methyl ethyl ketone, toluene, R.S. PhthaloBlue, and acrylic polymer) I8980 (product of Gibraltar Chemical 0.38Works identified as containing methyl ethyl ketone, toluene,isoindolinone yellow and acrylic polymer)

[0151] An additional decorative print layer is printed over the previousdecorative print layer at a coat weight of 0.8 gsm and dried in hot airat a temperature of 120° C. The paint composition used for thisdecorative print layer has the following formulation (all numericalvalues are in parts by weight): Component Parts Methylethyl ketone 42.85Methyl isobutyl ketone 39.1 VYHH 16.0 DP 80110 1.71 DP 36640 0.18 189770.18

[0152] The following paint composition is coated over the two driedprint coat layers at a coat weight of 30-32 gsm and dried in hot air ata temperature of 120° C. to provide a dry paint. In the following table,all numerical values are in parts by weight. Component Parts Methylethyl ketone 34 Toluene 16.7 VYHH 18.3 Edenol 9790 9 AVI-0301-3 Orange(product of Gibraltar 8.9 Chemical Works identified as containing methylethyl ketone, toluene, diarylide orange, VYHH and Edenol 9790)AVI-0301-5 Magenta (product of Gibraltar 5.3 Chemical Works identifiedas containing methyl ethyl ketone, toluene, Metal Azo Red, VYHH andEdenol 9790) AVI-0301-6 Iron Red (product of Gibraltar 3.7 ChemicalWorks identified as containing methyl ethyl ketone, toluene, Iron OxideRed, VYHH and Edenol 9790) AVI-0301-1 TiO₂ White (product of Gibraltar3.52 Chemical Works identified as containing methyl ethyl ketone,toluene, titanium dioxide, VYHH and Edenol 9790) AVI-0301-2 Carbon Black(product of 0.03 Gibraltar Chemical Works identified as containingmethyl ethyl ketone, toluene, carbon black, VYHH and Edenol 9790)

[0153] A pigmented pressure sensitive adhesive is then applied over thedry paint layer at a coat weight of 17 gsm using transfer lamination toprovide an adhesive layer corresponding to pressure sensitive adhesivelayer. The formulation for the pressure sensitive adhesive is asfollows: 96% by weight of a non-tackified acrylic emulsion containing across-linked copolymer of butyl acrylate and 2-ethyl hexyl acrylate,3.7% by weight UCD 1106E, and 0.3% by weight UCD 1507E.

EXAMPLE 5

[0154] A PET release liner is coated on one side with a silicone releasecoating. The thickness of the release coated liner is 0.92 mil.

[0155] A matte release coat is applied to the other side of the releaseliner using gravure at a coat weight of 4.4-4.6 gsm. The matte releasecoat is dried using forced hot air at a temperature of 149° C. Theformulation for the matte release coat is as follows (all numericalvalues are in parts by weight): Component Parts Methyl isobutyl ketone52.54 Elvacite 4402 (product of Lucite 20.98 International identified ashydroxy ethyl methacrylate modified acrylic resin) VYNS 1.35 Microtalc15-38 22.85 Byk 451 (product supplied by Byk 2.2 Chemie identified asblocked acid catalyst) Cymel 303 6.38

[0156] A transparent clear coat layer is applied to the matte releasecoat using a reverse roll coater at a coat weight of 13 gsm and driedusing forced hot air at a temperature of 120° C. The dry film thicknessis 0.4 mil. The formulation for the transparent clear coat layer is asfollows (all numerical values are in parts by weight): Component PartsRucothane CO-A-5002L (product 62.5 of Ruco Chemical identified aspolyester urethane) Toluene 18.75 Isopropanol 18.75

[0157] A decorative print layer is printed over the above indicatedtransparent film layer at a coat weight of 1 gsm and dried in hot air ata temperature of 120° C. The paint composition used for this decorativelayer has the following formulation (all numerical values are in partsby weight): Component Parts Methyl ethyl ketone 25.67 Methyl isobutylketone 22.0 VYHH 9.17 I8980 3.5 DP 37251 (product of Gibraltar Chemical0.99 Works identified as containing perylene red, methyl ethyl ketone,toluene and acrylic polymer) DP80110 1.0 DP39600 (product of GibraltarChemical 37.47 Works identified as containing TiO₂, methyl ethyl ketone,toluene and acrylic polymer) I8977 0.20

[0158] The following paint composition is coated over the decorativeprint layer at a coat weight of 66 gsm and dried in hot air at atemperature of 138° C. to form a dry paint layer. In the followingtable, all numerical values are in parts by weight: Component PartsMethyl isobutyl ketone 24.11 Toluene 20.65 VYHH 11.54 R-900 38.4Acryloid B-72 (product of Rohm and 3.86 Haas identified as an acrylicresin) I8980 2.6 DP37251 0.21 DP80110 0.40

[0159] A pressure sensitive adhesive is then applied over the dry paintlayer at a coat weight of 15-20 gsm using transfer lamination to providean adhesive layer. The pressure sensitive adhesive is a non-tackifiedacrylic emulsion. The formulation for the pressure sensitive adhesive isas follows: 70-90% by weight 2-ethyl hexyl acrylate, 1-10% by weightacrylic acid, and 10-20% by weight methyl acrylate.

EXAMPLE 6

[0160] A PET release liner is coated on one side with a silicone releasecoating. The thickness of the release coated liner is 0.92 mil.

[0161] A matte release coat is applied to the other side of the releaseliner using gravure. The release coat is dried using forced hot air at atemperature of 148.9° C. The matte release coat is applied at a coatweight of 4.0-5.0 gsm. The formulation for the matte release coat is asfollows (all numerical values are in parts by weight): Component PartsMethyl isobutyl ketone 42.03 Isopropanol 8.51 Microtalc 15-38 23.87Cymel 303 7.36 Cycat 4040 1.8 VROH (product supplied by 16.43 UnionCarbide identified as a vinyl chloride/vinyl acetate copolymer with OHfunctionality)

[0162] A transparent clear coat layer is applied over the matte releasecoat using a 2 mil byrd bar at a coat weight of 30 gsm and dried usinghot air at a temperature of 126.7° C. The formulation for thetransparent film layer is as follows (all numerical values are in partsby weight): Component Parts Water 7.98 N-methyl pyrrolidone 4.79 Texanol(product of Eastman 4.79 Chemicals identified as an ester alcohol) BYK333 (product of Byk Chemie 0.4 identified as a wetting agent) Vycar 351(product of Noveon identified 79.81 as a polyvinyl chloride copolymeremulsion) Antifoam PD-218 (product of Magrabar 0.32 Chemical identifiedas an antifoam agent) Rheolate 350 (product of Rheox, Inc. 1.92identified as a thickener)

[0163] The following paint composition is coated over the transparentclear coat film at a coat weight of 96 gsm and dried in hot air at atemperature of 126.7° C. to form a dry paint film layer. In thefollowing table, all numerical values are in parts by weight: ComponentParts Water 18.28 Surfynol CT-324 (product of Air 0.98 Productsidentified as a surfactant) R-900 32.88 Vycar 460X45 (product of Noveonidentified 34.72 as a vinyl chloride/acrylic copolymer) Vycar 460X46(product of Noveon identified 11.57 as a vinyl chloride/acryliccopolymer) Antifoam PD-218 0.19 Byk 333 0.23 Rheolate 350 1.2

[0164] A pressure sensitive adhesive layer is then applied over the drypaint layer at a coat weight of 17 gsm using transfer lamination toprovide an adhesive layer corresponding to pressure sensitive adhesivelayer. The formulation for the pressure sensitive adhesive is asfollows: 96% by weight of a non-tackified emulsion containing across-linked copolymer of butyl acrylate and 2-ethyl hexyl acrylate,3.7% by weight UCD 1106E, and 0.3% by weight UCD 1507E.

EXAMPLE 7

[0165] A PET release liner is coated on one side with a silicone releasecoat layer. The thickness of the release coated liner is 0.92 mil.

[0166] A matte release coat is applied to the other side of the releaseliner using gravure at a coat weight of 4.4-4.6 gsm. The formulation forthe matte release coat is as follows: 50.54 parts by weight methylisobutyl ketone, 7.84 parts by weight isopropanol, 8.93 parts by weightLankyd 13-1425, 10.68 parts by weight VAGH (product of Union Carbideidentified as hydroxy modified polyvinyl chloride/polyvinyl acetatecopolymer), 22 parts by weight Microtalc MP 15-38, 2 parts by weightCycat 4040, and 6.8 parts by weight Cymel 303. The matte release coat isdried using forced hot air at a temperature of 149° C.

[0167] A transparent clear coat layer is applied to the matte releasecoat using gravure at a coat weight of 12-16 gsm and dried using forcedhot air at a temperature of 165° C. The dry film thickness is 0.35-0.5mil. The formulation for this transparent film layer is as follows (allnumerical values are in parts by weight): Component Parts Cyclohexanone69.3 Elvacite 2042 10.5 Solsperse 17000 (product of Avecia 0.1identified as a wetting agent) Tinuvin 234 (product of Ciba identified0.6 as a light stabilizer) Kynar 301F (product of Atofina 27.0identified as a polyvinyl fluoride homopolymer) N-methyl-2-pyrrolidone2.5

[0168] A decorative print layer is printed over the transparent coatinglayer at a coat weight of 0.3-1.2 gsm and dried in hot air at atemperature of 105° C. The paint composition used for this decorativelayer has the following formulation (all numerical values are in partsby weight): Component Parts Methylethyl ketone 36.0 Methyl propyl ketone35.1 Kynar 7201 (SL) (product of Atofina 10.2 identified as a polyvinylfluoride copolymer) Elvacite 2010 (product of Lucite 3.4 Internationalidentified as a polymethyl methacrylate) Tinuvin 234 0.27 DP35740(product of Gibraltar 0.10 Chemical Works identified as a buff mixedmetal oxide pigment concentrate) DP35820 (product of Gibraltar 11.7Chemical Works identified as a brown mixed metal oxide pigmentconcentrate) DP39040 (product of Gibraltar 3.3 Chemical Works identifiedas a black mixed metal oxide pigment concentrate)

[0169] An additional decorative print layer is printed over the previousprinted decorative layer at a coat weight of 0.3-1.2 gsm and dried inhot air at a temperature of 105° C. The paint composition used for thisdecorative print layer has the following formulation (all numericalvalues are in parts by weight): Component Parts Methylethyl ketone 34.0Methyl propyl ketone 33.0 Kynar 7201 (SL) 9.6 Elvacite 2010 3.2 Tinuvin234 0.25 DP35740 14.4 DP35820 5.0 DP39040 3.2

[0170] The following paint composition is coated over the decorativeprint layers at a coat weight of 6-10 gsm and dried in hot air at atemperature of 105° C. to provide a dry paint film layer correspondingto dry paint film layer 110. In the following table, all numericalvalues are in parts by weight. Component Parts Methyl ethyl ketone 27.6Methyl propyl ketone 26.3 Kynar 7201 (SL) 7.4 Elvacite 2010 2.5 Tinuvin234 0.2 DP35740 4.1 DP35820 7.8 DP39040 0.6 DP39600 (product ofGibraltar 23.6 Chemical Works identified as a white titanium dioxidepigment concentrate)

[0171] A pigmented pressure sensitive adhesive is then applied over thedry paint layer at a coat weight of 17 gsm using transfer lamination toprovide an adhesive layer corresponding to pressure sensitive adhesivelayer 120. The formulation for the pressure sensitive adhesive is asfollows: 96% by weight of a non-tackified acrylic emulsion containing across-linked copolymer of butyl acrylate and ethyl hexyl acrylate, 3.7%by weight UCD 1106E, and 0.3% by weight UCD 1507E.

EXAMPLE 8

[0172] A PET release liner is coated on one side with a silicone releasecoating corresponding to the adhesive release coat layer. The thicknessof the release coated liner is 0.92 mil.

[0173] A matte release coat is applied to the other side of the releaseliner using gravure at a coat weight of 4.4-4.6 gsm. The formulation forthe matte release coat is as follows: 50.54 parts by weightmethylisobutyl ketone, 7.84 parts by weight isopropanol, 8.93 parts byweight Lankyd 13-1425, 10.68 parts by weight VAGH (product of UnionCarbide identified as hydroxy modified polyvinyl chloride/polyvinylacetate copolymer), 22 parts by weight Microtalc MP 15-38, 2 parts byweight Cycat 4040, and 6.8 parts by weight Cymel 303. The matte releasecoat is dried using forced hot air at a temperature of 149° C.

[0174] A decorative print layer is printed over the matte release coatat a coat weight of 0.3-1.2 gsm and dried in hot air at a temperature of105° C. The paint composition used for this decorative layer has thefollowing formulation (all numerical values are in parts by weight):Component Parts Methylethyl ketone 36.0 Methyl propyl ketone 35.1 Kynar7201 (SL) (product of Atofina 10.2 identified as a polyvinyl fluoridecopolymer) Elvacite 2010 (product of Lucite 3.4 International identifiedas a polymethyl methacrylate) Tinuvin 234 0.27 DP35740 (product ofGibraltar 0.10 Chemical Works identified as a buff mixed metal oxidepigment concentrate) DP35820 (product of Gibraltar 11.7 Chemical Worksidentified as a brown mixed metal oxide pigment concentrate) DP39040(product of Gibraltar 3.3 Chemical Works identified as a black mixedmetal oxide pigment concentrate)

[0175] An additional decorative print layer is printed over the previousprinted decorative layer at a coat weight of 0.3-1.2 gsm and dried inhot air at a temperature of 105° C. The paint composition used for thisdecorative print layer has the following formulation (all numericalvalues are in parts by weight): Component Parts Methylethyl ketone 34.0Methyl propyl ketone 33.0 Kynar 7201 (SL) 9.6 Elvacite 2010 3.2 Tinuvin234 0.25 DP35740 14.4 DP35820 5.0 DP39040 3.2

[0176] The following paint composition is coated using rotogravure overthe decorative print layers at a coat weight of 5-16 gsm and dried inhot air at a temperature of 105° C. to form a dry paint layer. In thefollowing table, all numerical values are in parts by weight. ComponentParts Toluene 19.0 Methyl ethyl ketone 23.6 VYHH 5.8 Edenol 9790 2.9DV39600 (product of Gibraltar 48.6 Chemical identified as iron oxide redpigment dispersion) DV39420 (product of Gibraltar 0.07 Chemicalidentified as carbon black pigment dispersion) DV36500 (product ofGibraltar 0.03 Chemical identified as Pigment Red 178 pigmentdispersion) DV34130 (product of Gibraltar 0.10 Chemical identified asPhtalo Blue RS pigment dispersion)

[0177] The following coating composition is coated over the dry paintlayer using roll coating at a coat weight of 20-30 gsm and dried in hotair at a temperature of 105° C. to form a support or reinforcing layer.In the following table, all numerical values are in parts by weight:Component Parts Toluene 14.1 Methyl ethyl ketone 21.1 VYHH 13.2 Edenol9790 6.6 DV39600 44.96 DV39420 0.04

[0178] A pigmented pressure sensitive adhesive is then applied over thecoated layer corresponding to support layer 180 at a coat weight of 17gsm using transfer lamination to provide an adhesive layer correspondingto pressure sensitive adhesive layer 120. The formulation for thepressure sensitive adhesive is as follows: 96% by weight of anon-tackified acrylic emulsion containing a cross-linked copolymer ofbutyl acrylate and 2-ethyl hexyl acrylate, 3.7% by weight UCD 1106E, and0.3% by weight UCD 1507E.

EXAMPLE 9

[0179]FIG. 10 illustrates one embodiment of the invention in which adecorative laminate 89 includes a dry paint layer coated in sequenceonto a release liner 30 which includes a matte release coat 32 on oneside and an adhesive release layer 34 on the side opposite the dry paintlayer. The dry paint layer comprises an outer clear coat layer 44, oneor more decorative print coats 48, and a color layer 22. A barrier layer60 is bonded to the color layer and a tie coat 90 is bonded to thebarrier coat and the PSA layer 28.

[0180] A PET liner is coated on one side with a silicone release coatingcorresponding to the adhesive release coat layer. The thickness of thesilicone coated liner is 0.92 mil and comprises Mitsubishi 92 gauge SLK.

[0181] The matte release coat is applied to the other side of therelease liner using gravure at a coat weight of 4.5 to 5.5 gsm. Theformulation for the matte release coat is as follows (with all numericalvalues in parts by weight): Component Parts Methyl isobutyl ketone(MiBK) 53.47 Isopropanol 6.49 Lankyd 13-1245 (product of Akzo 7.21Chemical, identified as an acrylic modified alkyd) VAGH 8.72 EFKA 5055(a carboxylic acid ester 1.10 dispersing agent) Microtalc MP 15-38 23.02Cymel 303 (Cytec melamine resin) 7.45 Byk 451 (Byk Chemie blocked acidcatalyst) 3.50

[0182] In preparing the release coat material the base materials (VAGH,alkyd and talc) are compounded in a 100 part formula. The Cymel 303 andByk 451 are later blended and after the materials are delivered to thecoater the two solutions are blended together. The matte release coat isdried using forced air at a temperature of 149° C.

[0183] The matte release coat comprises as its crosslinking resin themelamine (hexamethoxy methyl) resin Cymel 303. The hydroxyl modifiedpolyvinyl chloride/polyvinyl acetate copolymers (VAGH) comprise theprimary functional resin and the acrylic modified alkyd comprises asecondary functional resin. The primary crosslinking resin controlscrosslinking and bonds to the polyester carrier film. The secondaryfunctional resin modifies release of the dry paint layer (top coat) fromthe matte release coat. The blocked acid catalyst accelerates thecrosslinking process and the filler particles, talc, control the degreeof microroughness of the dry matte release coat.

[0184] A transparent clear coat layer is applied to the matte releasecoat using gravure at a coat weight of 2.6 to 3.0 gsm and dried usingforced hot air at a temperature of 165° C. The dry film thickness is0.09-0.10 mil. The clear coat consists essentially of a thermoplasticacrylic resinous material, preferably polymethyl methacrylate. Theformulation for the transparent top coat layer (with all numericalvalues in parts by weight) is as follows: Component Parts MEK 40 MiBK 41Elvacite 2042 19

[0185] One or more decorative print coats having printing inkformulations similar to those described in previous examples are nextprinted over the transparent top coat layer following procedures asdescribed previously.

[0186] The following paint coat composition comprises a plasticizedvinyl-based pigmented base coat having an epoxy stabilizer. The tie coatis coated over the decorative print layers, using roll coating at a coatweight of 33.0 to 36.0 gsm and dried in hot air at a temperature of 105°C. to form a color coat layer. The dry film thickness is 0.65 to 0.73mil. In the following table all numerical values are in parts by weight:Component Parts NiPar 820 (product of Angus Chemical 15.98 identified asa blend of 80% nitro propane and 20% nitro ethane) Xylene 23.95Cyclohexanone 7.71 VYHH 12.76 Edenol 9790 6.38 Stanclere T-883 (productof Adchross 0.06 Chemical identified as a tin heat stabilizer) EPON 828(epoxy resin product of Shell) 0.26 DV 39600 (Gibraltar TiO₂ white 32.12pigment dispersion) DV 396420 (Gibraltar carbon black 0.23 pigmentdispersion) DV 36500 (Gibraltar red pigment 0.16 dispersion) DV 34130(Gibraltar phthalo blue 0.39 pigment dispersion)

[0187] The following barrier coat layer is coated over the dried colorcoat layer at a coat weight of 1.5 to 2.0 gsm. All numerical values arein parts by weight: Component Parts Adcoat 61WG178 (a product of Rohm 45and Haas identified as acrylic polymer) Isopropanol 52 Cymel 303 (Cytecmelamine resin) 2.4 Cycat 4040 (Cytec paratoluene 0.2 sulfonic acid)

[0188] The barrier layer comprises a cross-linked acrylic resinousmaterial which is applied by gravure and dried, using forced air at atemperature of 149° C. The dry film thickness of the barrier layer is0.05 to 0.07 mil.

[0189] As mentioned previously, the barrier layer provides a means forinhibiting or preventing migration of discoloration-causing pigmentsinto the color-producing layers of the laminate.

[0190] The following tie coat is coated over the dried barrier layer.All numerical values are in parts by weight: Component Parts MEK 25.24MiBK 25.59 VYHH 8.98 Edenol 9790 plasticizer 4.49 Stanclere T-883 0.04EPON 828 0.18 DV 39600 35.03 DV 39420 0.45

[0191] The tie coat is coated at a coat weight of 2.8 to 3.3 gsm andwith a dry film thickness from about 0.05 to 0.06 mil. The tie coatenhances adhesion between the barrier layer and the pressure sensitiveadhesive layer. The tie coat is a variation of the color coat. In thepresent system, the barrier layer adheres to the color coat and the PSAadheres well to a similar color coat; so the tie coat is selected forits ability to provide good adhesion between the color coat and the PSA.The pigment component of the tie coat hardens the binder to a usefullevel.

[0192] The dry film thickness of the decorative laminate of this Exampleis within a preferred range of 1.30 to 1.60 mil. In the describedexample, the dry film thickness of the combined top coat, color coat,barrier coat, tie coat and PSA is from 1.35 to 1.51 mil.

[0193] A pigmented pressure sensitive adhesive layer is then applied toa carrier at a coat weight of 13 to 16 gsm. The dry film thickness ofthe PSA is from about 0.45 to 0.55 mil. The PSA is then applied to thetie coat by transfer lamination. The PSA is available from AveryDennison Corporation under product no. S-3526 and the formulation forthe PSA is as follows (with numerical values in parts by weight):Component Parts S-3506 (product of Avery Dennison, 96.0 PerformancePolymers, identified as a cross-linked copolymer emulsion of butylacrylate and 2-ethyl hexyl acrylate) UCD 110GE (white TiO₂ pigment 3.7dispersion from Rohm and Haas) UCD 1507E (carbon black pigment 0.3dispersion from Rohm and Haas)

EXAMPLE 10

[0194] Gloss measurements taken on the Byk-Mallinckrodt gloss meter forvarious paint films as described herein produced the following glossreadings:

[0195] (1) Release coat—Elvacite 2899/VYNS at a ratio of 14.5:1, havinga standard range of microtalc at 1.0 to 1.1:1 talc to polymer with Cymel303

[0196] Top coat—none

[0197] Color coat—Rohm and Haas Acryloid B72/VYHH at a ratio of 1:3

[0198] Gloss at 60°—3.4

[0199] Gloss at 85°—8.8

[0200] (2) Release coat—Elvacite 2899/VYNS at a ratio of 14.5:1, havinga standard range of microtalc at 1.0 to 1.1:1 talc to polymer with Cymel303

[0201] Top coat—Rucothane CO A 5002L urethane polymer

[0202] Color coat—Rohm and Haas B72/VYHH at a ratio of 1:3

[0203] Gloss at 60°—4.9

[0204] Gloss at 85°—8.5

[0205] (3) Film having faux leather finish:

[0206] Release coat—Acrylic modified alkyd with Cymel 303 and standardrange of microtalc at 1.0 to 1.1:1 talc to polymer.

[0207] Top coat—Elvacite 2042 and VYHH/Vitel 220B at 1:1 ratio.

[0208] Gloss at 60°—2.2

[0209] Gloss at 85°—32.4

[0210] (4) Films having release coats and transparent top coat layersprepared according to Examples 7 and 9 produced gloss readings within arange from about 26 to about 30 at 85°.

EXAMPLE 11

[0211] To measure the “force differential” in terms of carrier releaseforce versus unwind release force, samples were produced intwo-inch-wide by 12-inch long strips to simulate unwinding of a roll ofthe decorative film. A construction under test comprised the FIG. 3embodiment having a transparent top coat, pigmented color layer, a PSAlayer with the PSA side of the film exposed, and a release linercomprising a PET film having a matte release coat in contact with thetop coat and an exposed silicone release coat on the opposite side ofthe release liner. In other tests, the construction was similar to thatshown in FIG. 10 in which the same construction included the barrierlayer and the tie coat layer.

[0212] One comparative test used test samples in which the compositionsof the transparent top coat, the color coat and the PSA layer weregenerally as described in Examples 7 and 9, which included the AveryDennison S-3506 PSA layer (an unpigmented form of Avery S-3526adhesive). In other test samples, color coat and top coat formulationssimilar to Example 1 were used, in combination with the Avery S-3506 PSAlayer. In further test samples, a construction involved the top coat andcolor coat formulations of Example 1 along with a different AveryDennison PSA identified as S-692N adhesive.

[0213] The tests involved peeling the matte release layer away from thedry paint layer and peeling the silicone side of the release liner awayfrom the PSA part of the sample. The tests were conducted at roomtemperature. In one test, separate adhesive tapes were attached to thesides of the test samples to test the peel force at each interface witheach tape extending in opposite directions, each at a 90° angle to thesample. The tests were performed on a movable sled having adjustablepeel rates which, in one embodiment, were varied in increments fromspeeds as low as 12 inches per minute up to 1200 inches per minute. Peelforces were measured at progressive speed intervals and plotted oncomparative force-versus-peel rate profiles.

[0214] The test results showed that carrier release force is reasonablyuniform across a broad range of release rates, whereas unwind releaseforces tend to stay below the carrier release force at low speeds, butthey approach and ultimately exceed the carrier force at higher speeds.Each profile generated by the tests was characterized by a cross-overrelease rate at which the unwind release force reaches and exceeds thecarrier release force. Generally speaking, the self wound rolls thatproduced the best unwind response maintained a carrier release force inexcess of the unwind release force at rates up to about 100 inches perminute. The test results showed that unwind force for the S-692N PSAapproached carrier release force more rapidly than and exceeded it at amuch lower propagation rate than the S-3506 PSA, which had superiorunwind performance compared to the S-692N PSA. Such superior unwindperformance was characterized by self-wound rolls of film containing theS-3506 adhesive being unwound without premature release of the releaseliner from the dry paint layer; whereas rolls of film containing theS-692N PSA experienced unreliable release response.

[0215] It was also observed that the S-3506 PSA exhibited lower tacklevels and had less cold flow than the S-692N PSA. This was attributedto the S-3506 PSA having an internally cross-linked structure whichproduced the lower tack levels and lower cold flow than the S-692N PSAwhich was not internally cross-linked and had higher tack levels, aswell as higher cold flow. This difference in PSA properties caused thenon-cross-linked PSA to stick more to the silicone side of the releaseliner and raised the unwind release force to levels that were too highand produced unreliable unwind response compared to the cross-linked PSAwhich produced more desirable (lower) unwind release force levels.

EXAMPLE 12

[0216] Test panels containing barrier coats were prepared and tested forcolor shift. The test panels included a blue color layer similar to thecolor layer of Example 9 and a cross linked acrylic PSA layer, Avery'sS-3506, similar to the PSA used in Example 9. The test films wereapplied to a yellow (Hansa Yellow 10G) painted surface and subjected toaccelerated aging. The test films were measured for discoloration (colorshift) caused by migration of azo-type color constituents that passedfrom the painted surface through the PSA layer to the color layer of thetest sample. The test panels were prepared by using a dry paint colorlayer containing a plasticized vinyl-based paint layer containing adispersed blue pigment. The S-3506 PSA was applied to the color layer. Amedium yellow painted substrate was prepared using Behr 1300 deep base(5 ounces medium yellow per gallon base) applied at 7.5 mils wet coatingto 3 mil polyester. The paint coat was allowed to dry for three hoursminimum at room temperature then force air dried for five minutes at250° F. The C.I.E. test procedures were used to measure Δ b* colorchange on the test panel at 60° C.

[0217] The following table shows six separate barrier coatings whichwere evaluated for color shift using these test procedures. Test sample1 was a cross-linked low molecular weight acrylic barrier coat; testsamples 2 and 3 were thermoplastic low molecular weight acrylic barriercoats containing filler or additive materials for reducing colortransmission; test samples 4 and 5 were thermoplastic low-molecularweight acrylic barrier layers that included the filler or additivematerials, but also included PVP as an adhesion promoter; and testsample 6 was a high molecular weight thermoplastic acrylic barrier coatin the absence of any additive, filler or adhesion promoter. Thematerials contained in each test sample are shown in parts by weight.Barrier Coat Test Samples Materials #1 #2 #3 #4 #5 #6 Adcoat 61WG17845.0 54.2 61.5 46.5 44.7 acrylic Degussa Alum. Ox. 2.5 0.9 2.1 0.7 HaloxXtain A 2.5 0.9 2.1 0.7 IPOH 52.4 40.8 36.7 35.0 26.6 20.0 Cymel 303 2.4Cycat 4040 0.2 PVP K80 14.3 27.3 Toluene 70.7 Elvacite 2041 9.3 acrylic

[0218] The following test results for test samples #1 through #6 showcolor shift data for PSAs applied by both direct coating and bytransfer-lamination. Test Samples Materials #1 #2 #3 #4 #5 #6 Coatweight (gsm) 1.6 4.9 4.7 2.6 2.4 0.8 Direct adhesion good good good goodgood good Color change 60° C. 0.38/ 0.37/ 0.35/  0.4/ (Δb*) 1170 hrs 552hrs 1002 hrs 1002 hrs Transfer- poor poor poor good good good laminationadhesion Color change 60° C. 0.47/ 0.97/ 0.61/ 0.89/ 0.39/ 0.38/ (Δ b*) 162 hrs 239 hrs 330 hrs 201 hrs  376 hrs  552 hrs

[0219] A similar test was conducted using the cross-linked acrylicbarrier coat of test sample #1 with the following tie coat (in parts byweight): Tie Coat Material Parts MEK 25.22 MiBK 25.59 Dow VYHH 8.98Plastolein 9790 4.49 Stanclere T-883 0.04 Dow EPON 828 0.18 DV39600(Gibraltar White) 35.30 DV29420 (Gibraltar Black 0.45 Disp.) MiBK 4.00

[0220] The product having the tie coat was tested as 60° C. for 401hours. Samples for color shift measurement were taken throughout theroll. An average of 0.24 Δb* color change resulted with a standarddeviation of 0.06. The tie coating was used in this test because theadhesive was applied by transfer-lamination, and the tie coat was neededto increased adhesion between the barrier coat and the pressuresensitive adhesive.

[0221] Similar barrier polymer tests were conducted in which the C.I.E.Δb* color shift was measured for different test samples, and then thecolor change that would occur at 60° C. for 16 days was estimated. Coatwt. Final Proj. Barrier Polymer (gsm) Hrs. 16 days (1) Thermoplasticacrylic - R & H 2.5 400 1.82      61WG178 (2) Same as (1) 2.5 308 4.86(3) Cross-linked acrylic - R & H 1.8 1337 0.25      61WG178/15 phr Cymel303/1 phr      Cycat 4040 (4) Same as (3) 1.6 497 0.37 (5) Same as (3)1.6 227 0.96 (6) Cross-linked acrylic - R & H 1.8 1337 0.30     61WG178/10 phr Cymel 303/1 phr      Cycat 4040 (7) Cross-linkedacrylic - R & H 1.6 487 0.22      61WG178/15 phr Cymel 303/1 phr     Cycat 4040/5 phr Ti02/9 phr AlO_(x) (8) Thermoplastic acrylic - R & H2.0 427 0.12      61 WG 178/15 phr AlO_(x)/15 phr      Xtain

[0222] General observations from these tests are that cross-linking ofthe low molecular weight acrylic barrier layer produces good color shiftimprovements into the acceptable range. Addition of titanium dioxide,aluminum oxide and similar metal compounds and oxides and salts furtherimprove the barrier properties of both thermoplastic and cross-linkedpolymeric barrier layers.

[0223] The present invention has been described with respect tomultilayer laminates used as a wall film for interior architecturalapplications, but the laminate also is useful in other applications aswell. These would include exterior architectural applications such assiding panels and wall surfaces; outdoor decorative items and signs;interior automotive decorative and functional uses such as dashboardsand panels; and exterior automotive uses including automotive bodyparts, trim parts and panels.

What is claimed is:
 1. A multi-layer decorative laminate for applying alayer of color to a substrate surface, the laminate comprising: a drypaint layer comprising a color layer which includes a binder and apigment, the dry paint layer having an upper surface and a lowersurface, a pressure-sensitive adhesive layer overlying the upper surfaceof the dry paint layer and adapted for adhering the laminate to asubstrate surface at room temperature; a release liner overlying thelower surface of the dry paint layer, the release liner removable fromthe dry paint layer at room temperature for exposing an outer surface ofthe dry paint layer when the pressure-sensitive adhesive layer adheresthe laminate to the substrate surface under application of pressure andthe release liner is peeled away from the dry paint layer; and a thinflexible barrier layer disposed between the adhesive layer and the colorlayer, the barrier layer made from a material that inhibits migration ofor captures migrating discoloration-causing pigments from a paintedsurface of the substrate through the adhesive layer to the color layersufficiently to essentially prevent noticeable color change caused bythe migrating pigments from occurring in the color layer under roomtemperature conditions.
 2. The article according to claim 1 in which thebarrier layer material inhibits or captures migrating mono azodiscoloration-causing pigments.
 3. A multi-layer decorative laminate forapplying a layer of color to a substrate surface, the laminatecomprising: a dry paint layer comprising a color layer which includes abinder and a pigment, the dry paint layer having an upper surface and alower surface, a pressure-sensitive adhesive layer overlying the uppersurface of the dry paint layer and adapted for adhering the laminate toa substrate surface at room temperature; a release liner overlying thelower surface of the dry paint layer, the release liner removable fromthe dry paint layer at room temperature for exposing an outer surface ofthe dry paint layer when the pressure-sensitive adhesive layer adheresthe laminate to the substrate surface under application of pressure andthe release liner is peeled away from the dry paint layer; and a thinflexible barrier layer disposed between the adhesive layer and the colorlayer, the barrier layer made from a material that inhibits migration ofor captures migrating discoloration-causing azo-type pigments from apainted surface of the substrate through the adhesive layer to the colorlayer, in which the barrier material has a dry film thickness of notmore than about 10% of the total thickness of the decorative laminate(exclusive of the release liner).
 4. A multi-layer decorative laminatefor applying a layer of color to a substrate surface, the laminatecomprising: a dry paint layer comprising a color layer which includes abinder and a pigment, the dry paint layer having an upper surface and alower surface, a pressure-sensitive adhesive layer overlying the uppersurface of the dry paint layer and adapted for adhering the laminate toa substrate surface at room temperature; a release liner overlying thelower surface of the dry paint layer, the release liner removable fromthe dry paint layer at room temperature for exposing an outer surface ofthe dry paint layer when the pressure-sensitive adhesive layer adheresthe laminate to the substrate surface under application of pressure andthe release liner is peeled away from the dry paint layer; and a thinflexible barrier layer disposed between the adhesive layer and the colorlayer, the barrier layer comprising an acrylic resinous material and afine particulate additive comprising a metal compound, a metal oxideand/or a metal salt dispersed in the acrylic resinous material in anamount that reduces migration of or captures migratingdiscoloration-causing pigments from a painted surface of the substratethrough the adhesive layer to the color layer.
 5. The article accordingto claim 4 in which the barrier layer material inhibits or capturesmigrating mono azo discoloration-causing pigments.
 6. A self-woundmulti-layer laminate for applying a layer of color to a substratesurface, the laminate comprising: a dry paint layer comprising a colorlayer which includes a binder and a pigment, the dry paint layer havingan upper surface and a lower surface, a pressure-sensitive adhesivelayer overlying the upper surface of the dry paint layer and adapted foradhering the laminate to a substrate surface at room temperature; arelease liner overlying the lower surface of the dry paint layer, therelease liner having a matte release coat releasably adhered to thelower surface of the dry paint layer, and an adhesive release coat layeron a side of the release liner opposite from the dry paint layer, therelease liner and the matte release coat removable from the dry paintlayer at room temperature, the matte release coat transferring a mattefinish to an exposed surface of the dry paint layer when thepressure-sensitive adhesive layer adheres the laminate to the substratesurface under application of pressure and the release liner is peeledaway from the dry paint layer, the laminate adapted for being self-woundinto a roll with the pressure-sensitive adhesive layer in contact withthe adhesive release coat layer, the adhesive release coat layer and thepressure-sensitive adhesive layer having an unwind release force betweenthem which is lower that a carrier release force between the matterelease coat and the dry paint layer, such that the adhesive releasecoat preferentially releases the liner from contact with thepressure-sensitive adhesive layer when unwinding the laminate from itsroll form, while the matte release coat maintains contact with the drypaint layer when the laminate is being unwound from its roll form, and abarrier layer disposed between the adhesive layer and the color layerand made from a material that inhibits migration of or capturesmigrating discoloration-causing pigments from a painted surface to whichthe adhesive side of the laminate is adhered, the barrier material madeof a composition adapted to essentially prevent noticeable color changecaused by the migrating pigments from occurring in the color layer underroom temperature conditions.
 7. The article according to claim 6 inwhich the barrier layer material inhibits or captures migrating mono azodiscoloration-causing pigments.
 8. A process for making a multi-layerdecorative laminate for applying a layer of color to a substratesurface, the process comprising: forming a dry paint layer on a releaseliner, the dry paint layer comprising a color layer which includes abinder and a pigment, the dry paint layer having an upper surface and alower surface, applying a pressure-sensitive adhesive layer to the uppersurface of the dry paint layer, the adhesive layer adapted for adheringthe laminate to a substrate surface at room temperature; the releaseliner overlying the lower surface of the dry paint layer, the releaseliner removable from the dry paint layer at room temperature forexposing an outer surface of the dry paint layer when thepressure-sensitive adhesive layer adheres the laminate to the substratesurface under application of pressure and the release liner is peeledaway from the dry paint layer; and applying a thin flexible barrierlayer between the adhesive layer and the color layer, the barrier layermade from a material that inhibits migration of or captures migratingdiscoloration-causing azo-type pigments from a painted surface of thesubstrate through the adhesive layer to the color layer sufficiently toessentially prevent noticeable color change caused by the migratingpigments from occurring in the color layer under room temperatureconditions.
 9. The process according to claim 8 in which the adhesivelayer is direct-coated on the barrier layer.